Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same

ABSTRACT

This invention relates to supported and nonsupported catalyst components comprising (a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and the anion containing at least one subtituent comprising a moiety having an active hydrogen reacted with (c) an organometal or metalloid compound wherein the metal or metalloid is selected from Groups 2, 12, 13, or 14 of the Periodic Table of the Elements, and, optionally, (b) a transition metal compound, (d) a support material, and/or a diluent. Included are methods for preparation of the catalyst components, catalysts, reaction products and dispersions thereof, as well as polymerization process using the catalyst.

CROSS REFERENCE STATEMENT

This application claims the benefit of priority under 35 U.S.C. §371 ofPCT/US97/21875, filed Dec. 1, 1997, which was published under PCTArticle 21(2) in English, and which is a continuation-in-part of U.S.application Ser. No. 08/768,518, filed Dec. 18, 1996, now U.S. Pat. No.5,783,512.

FIELD OF THE INVENTION

This invention relates to a catalyst component dispersion comprising anionic compound in solid form, to a nonsupported solid catalystcomprising a transition metal compound, an ionic compound, and anorganometal compound, to a supported solid catalyst comprising atransition metal compound, an ionic compound, an organometal compound,and a support material, to a method for preparing the catalyst componentdispersion, to a method for preparing the solid catalysts, to a methodfor activating a catalyst suitable for addition polymerization, and toan addition polymerization process using the solid catalysts.

BACKGROUND OF THE INVENTION

Homogeneous ionic transition metal catalysts are known for their highcatalytic activity in addition polymerizations, especially those ofolefins and diolefins, and are capable of providing olefinic polymers ofnarrow molecular weight distributions and, for example when ethylene iscopolymerized with a further alpha-olefin, narrow comonomerdistributions. Under polymerization conditions where polymer is formedas solid particles, for example, in gas phase or slurry phasepolymerizations, these homogeneous (soluble) catalysts form polymerdeposits on reactor walls and stirrers which deposits should be removedfrequently as they prevent an efficient heat-exchange necessary forcooling the reactor contents, prevent the regular or continuous removalof polymer from the reactor, and cause excessive wear of the movingparts in the reactor. The polymers produced by these soluble catalystsfurther have undesirable particle characteristics such as a low bulkdensity which limits the commercial utility of both the polymer and theprocess. Therefore, there is a need to provide catalysts that wouldovercome such problems.

Several supported catalysts have been proposed for use in particleforming polymerization processes. Support materials in the prior art aretypically employed in combination with catalytic components to obtainthe formation of polymer particles of desirable particle size andmorphology. Secondly, support materials are used to increase catalyticactivity per unit of active components by depositing such components ona support material having a relatively high surface area. Furthermore,support materials are employed for anchoring thereon the catalyticcomponents to avoid the presence of significant amounts of catalystwhich under particle forming polymerization conditions becomessolubilized and gives rise to particles of undesired size and morphologysaid particles contributing to the formation of polymer deposits atreactor walls and other moving parts in the reactor.

EP-327649 and EP-725086 describe solid catalysts using alumoxanes ascocatalyst. EP-327649 relates to a nonsupported olefin polymerizationcatalyst composed of a transition metal compound and an alumoxane havingan average particle size of 5 to 200 micrometers and a specific surfacearea of 20 to 1,000 m²/g. EP-725086 describes a solid component of acatalyst for ethylene and alpha-olefins (co)polymerization comprising ametallocene supported on an inorganic solid carrier, where a carbon atomof one of the η⁵-cyclopentadienyl rings coordinated to the transitionmetal is covalently bonded to a metal atom of the inorganic solidcarrier. This solid component is typically used with an organic aluminumoxy-derivative which is usually alumoxane.

Supported nonalumoxane catalysts are disclosed, for example, inEP-418044, EP-522581, WO-91/09882, WO-94/03506, WO-9403509, andWO-9407927. These describe supported catalysts obtained by combining atransition metal compound, an activator component comprising a cationcapable of reacting with a transition metal compound and a bulky, labileanion capable of stabilizing the metal cation formed as a result ofreaction between the metal compound and the activator component, and acatalyst support material. In EP-522581 and WO-9407927 additionally anorganometal compound, typically an organoaluminum compound is employed.

EP-727443 describes an olefin polymerization catalyst obtainable bycontacting a transition metal compound, an organometallic compound, anda solid catalyst component comprising a carrier and an ionized ioniccompound capable of forming a stable anion on reaction with saidtransition metal compound, wherein said ionized ionic compound comprisesa cationic component and an anionic component and said cationiccomponent is fixed on the surface of the carrier.

WO-96/04319 describes a catalyst composition comprising a metal oxidesupport having covalently bound to the surface thereof directly throughthe oxygen atom of the metal oxide, an activator anion that is alsoionically bound to a catalytically active transition metal compound.

WO-93/11172 relates to polyanionic moieties comprising a plurality ofnoncoordinating anionic groups pendant from and chemically bonded to acore component. The core component may be a cross-linked polystyrene orpolydivinylbenzene polymeric core or a polyanionic Lewis basic coresubstrate reactable with a Lewis acid. The polyanionic moieties are usedin a noncoordinating association with cationic transition metalcompounds.

Copending U.S. application Ser. No. 08/610,647, filed Mar. 4, 1996, U.S.Pat. No. 5,834,393 corresponding to WO-96/28480, describes supportedcatalyst components comprising a support material, an organometalcompound, an activator compound comprising a cation which is capable ofreacting with a transition metal compound to form a catalytically activetransition metal complex and a compatible anion having up to 100nonhydrogen atoms and containing at least one substituent comprising amoiety having an active hydrogen. When combined with a transition metalcompound, the resulting supported catalysts are very useful additionpolymerization catalysts.

It would be desirable to provide a solid catalyst and solid catalystdispersions, and components or precursors therefore which do not requirean alumoxane component and which can be used in particle formationpolymerization processes without requiring a support material.

It would also be desirable to provide a solid catalyst, includingprecursors therefor, which when used in a polymerization process arecapable of producing polymers at good catalyst efficiencies.

It is a further object to provide a solid catalyst, including precursorstherefore which when used in a particle forming polymerization processgive reduced amounts of particles of undesired size and morphology. Itis yet a further object to provide a solid catalyst, includingprecursors therefore, which when used in a particle formingpolymerization process prevents or largely removes the problem offormation of polymer deposits at reactor walls and other moving parts inthe reactor.

It is yet a further object to provide a solid catalyst andpolymerization process that is capable of forming polymers in the formof free flowing powder or particles.

It is another object to provide a method for making a solid catalystwithout requiring recovery or purification steps.

It is a further object to provide a solid catalyst which furthercomprises a support material.

One or several of these objects are accomplished by the embodiments ofthe present invention described hereinafter.

SUMMARY OF THE INVENTION

In one aspect of this invention there is provided a dispersion of asupported catalyst component comprising (a) an ionic compound comprising(a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atomsand the anion containing at least one substituent comprising a moietyhaving an active hydrogen and (d) a support material, wherein thesupported catalyst component is in solid form dispersed in a diluent inwhich both (a) and (d) are insoluble or sparingly soluble, and wherein,

(i) the support material is a pretreated support material and in thesupported catalyst component the anion (a)(2) is not chemically bondedto the support (d), or

(ii) the ionic compound has a solubility in toluene at 22° C. of atleast 0.1 weight percent, the support material used is a supportmaterial containing tethering groups and in the supported catalystcomponent the anion (a)(2) is chemically bonded to the support (d).

In a related aspect there is provided a dispersion of a nonsupportedcatalyst component comprising (a) an ionic compound comprising (a)(1) acation and (a)(2) an anion having up to 100 nonhydrogen atoms and theanion containing at least one substituent comprising a moiety having anactive hydrogen, wherein (a) is in solid form in the absence of asupport material and is dispersed in a diluent in which (a) is insolubleor sparingly soluble.

Desirable embodiments of the aforementioned dispersions are thosewherein the catalyst component further comprises (b) a transition metalcompound and wherein the catalyst component is a substantially inactivecatalyst precursor; or wherein the catalyst component further comprises(c) an organometal or metalloid compound wherein the metal or metalloidis selected from the Groups 1-14 of the Periodic Table of the Elementsand the catalyst component is a reaction product of (a) and (c), whilein other desirable embodiments the catalyst component excludes (b) atransition metal compound, excludes (c) an organometal or metalloidcompound wherein the metal or metalloid is selected from the Groups 1-14of the Periodic Table of the Elements, or excludes both (b) and (c).

In another aspect of this invention there is provided a nonsupportedcatalyst comprising, in the absence of a support material, (a) an ioniccompound comprising (a)(1) a cation and (a)(2) an anion having up to 100nonhydrogen atoms and the anion containing at least one substituentcomprising a moiety having an active hydrogen, (b) a transition metalcompound, and (c) an organometal or metalloid compound wherein the metalis selected from the Groups 1-14 of the Periodic Table of the Elements.

In an other aspect of this invention there is provided a supported solidcatalyst comprising (a) an ionic compound comprising (a)(1) a cation and(a)(2) an anion having up to 100 nonhydrogen atoms and the anioncontaining at least one substituent comprising a moiety having an activehydrogen, (b) a transition metal compound, (c) an organometal ormetalloid compound wherein the metal or metalloid is selected from theGroups 1-14 of the Periodic Table of the Elements, and (d) a supportmaterial, wherein,

(i) the support material is a pretreated support material and in thesupported catalyst component the anion (a)(2) is not chemically bondedto the support (d), or

(ii) the ionic compound has a solubility in toluene at 22° C. of atleast 0.1 weight percent, the support material used is a supportmaterial containing tethering groups and in the supported catalystcomponent the anion (a)(2) is chemically bonded to the support (d); and,

wherein the solid catalyst is obtained by combining components (a), (b),(c), and (d) in any order, and wherein, during at least one step in thepreparation of the solid catalyst, component (a) is dissolved in adiluent in which (a) is soluble, optionally in the presence of one ormore of components (b), (c), and (d) or the contact product of (a) withsuch one or more of (b), (c), and (d), and then is converted into solidform.

In the aforementioned aspects relating to a nonsupported catalyst and toa supported catalyst, desirable embodiments are those wherein the anion(a)(2) corresponds to Formula (II):

[M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II)

wherein:

M′ is a metal or metalloid selected from Groups 5-15 of the PeriodicTable of the Elements;

Q independently in each occurrence is selected from the group consistingof hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl,and substituted-hydrocarbyl radicals, including halo-substitutedhydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-substitutedorgano-metalloid radicals, the hydrocarbyl portion in each of thesegroups preferably having from 1 to 20 carbons, with the proviso that innot more than one occurrence is Q halide; G is a polyvalent hydrocarbonradical having r+1 valencies bonded to M′ and r groups (T—H);

the group (T—H) is a radical wherein T comprises O, S, NR, or PR, the O,S, N of P atom of which is bonded to hydrogen atom H wherein R is ahydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical or hydrogen;

m is an integer from 1 to 7;

n is an integer from 0 to 7;

q is an integer of 0 or 1;

r is an integer from 1 to 3;

z is an integer from 1 to 8;

d is an integer from 1 to 7; and

n+z−m=d, and

where the cation (a)(1) of ionic compound (a) is represented by thefollowing general formula:

[L*—H]⁺,

wherein:

L* is a nitrogen, oxygen. sulfur or phosphorus containing Lewis basecontaining from one to three C₁₀₋₄₀ alkyl groups with a total of from 12to 100 carbons.

When the catalysts of the present invention include a support material(d) the versatility of the catalyst is improved. Employing a supportmaterial allows the particle size of the solid catalyst to be variedbetween wider ranges.

In another aspect of this invention there is provided a method forpreparing a dispersion of a supported catalyst component comprising (a)an ionic compound comprising (a)(1) a cation and (a)(2) an anion havingup to 100 nonhydrogen atoms and the anion containing at least onesubstituent comprising a moiety having an active hydrogen, and (d) asupport material, where the supported catalyst component is in solidform dispersed in a diluent in which both (a) and (d) are insoluble orsparingly soluble, the method comprising converting a solution of theionic compound (a) in a diluent in which (a) is soluble in the presenceof the support material into a dispersion comprising component (a) insolid form, and wherein,

(i) the support material used is a pretreated support material and, inthe supported catalyst component, the anion (a)(2) is not chemicallybonded to the support (d), or

(ii) the ionic compound used has a solubility in toluene at 22° C. of atleast 0.1 weight percent, the support material used is a supportmaterial containing tethering groups and, in the supported catalystcomponent, the anion (a)(2) is chemically bonded to the support (d).

In another aspect of this invention there is provided a method forpreparing a dispersion of a nonsupported catalyst component comprisingconverting a solution of an ionic compound (a) comprising (a)(1) acation and (a)(2) an anion having up to 100 nonhydrogen atoms and theanion containing at least one substituent comprising a moiety having anactive hydrogen, in a diluent in which (a) is soluble in the absence ofa support material into a dispersion comprising component (a) in solidform.

In another aspect of this invention there is provided a method forpreparing a solid catalyst comprising combining, in any order, (a) anionic compound comprising (a)(1) a cation and (a)(2) an anion having upto 100 nonhydrogen atoms and the anion containing at least onesubstituent comprising a moiety having an active hydrogen, (b) atransition metal compound, (c) an organometal or metalloid compoundwherein the metal or metalloid is selected from the Groups 1-14 of thePeriodic Table of the Elements, and, optionally, (d) a support material,wherein during at least one step in the preparation of the solidcatalyst, component (a) is dissolved in a diluent in which (a) issoluble to produce a solution of (a), optionally in the presence of oneor more of components (b), (c), and (d) or the contact product of (a)with such one or more of (b), (c), and (d), and then is converted intosolid form, optionally followed by recovering the solid catalyst in dryparticulate form, wherein, when a support material (d) is present,

(i) the support material used is a pretreated support material and inthe supported catalyst the anion (a)(2) is not chemically bonded to thesupport (d), or

(ii) the ionic compound used has a solubility in toluene at 22° C. of atleast 0.1 weight percent, the support material used is a supportmaterial containing tethering groups and in the supported catalyst theanion (a)(2) is chemically bonded to the support (d).

A highly desirable embodiment of this method for preparing a solidcatalyst is that wherein the support material used is a pretreatedsupport material with a pore volume of from 0.1 to 5 cm³/g and in thesupported catalyst the anion (a)(2) is not chemically bonded to thesupport ((1), and wherein the volume of the solution of (a), optionallyin the presence of one or both of (b) and (c), is from 20 volume percentto 200 volume percent of the total pore volume of the support materialused, and wherein the solid catalyst is produced by adding the solutionof (a) to substantially dry pretreated support material, followed byremoval of the diluent.

An alternative embodiment of this method for preparing a solid catalystis that wherein during the at least one step in the preparation of thesolid catalyst, a dispersion comprising component (a) in solid form isgenerated by cooling a solution of (a) in a diluent in which (a) issoluble, by contacting a solution of (a) in a diluent in which (a) issoluble with a diluent in which (a) is insoluble or sparingly soluble,by evaporating diluent from a solution of (a), by adding one or moreprecipitating agents to a solution of (a), or a combination of two ormore of these techniques.

In another aspect of this invention there is provided a method foractivating a substantially inactive catalyst precursor to form acatalyst suitable for addition polymerization wherein a substantiallyinactive catalyst precursor comprising (a) an ionic compound comprising(a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atomsand the anion containing at least one substituent comprising a moietyhaving an active hydrogen, (b) a transition metal compound, and,optionally, (d) a support material, is contacted with (c) an organometalor metalloid compound, where the metal or metalloid is selected fromGroups 1-14 of the Periodic Table of the Elements, to form an activecatalyst.

In another aspect of this invention there is provided and additionpolymerization process wherein one or more addition polymerizablemonomers are contacted with one of the aforementioned solid catalystsunder addition polymerization conditions.

In another aspect of this invention there is provided an ionic compound(a) comprising (a)(1) a cation and (a)(2) an anion having up to 100nonhydrogen atoms and the anion containing at least one substituentcomprising a moiety having an active hydrogen, where the cation (a)(1)is represented by the following general formula:

[L*—H]⁺,

wherein:

L* is a nitrogen, oxygen, sulfur or phosphorus containing Lewis basecontaining from one to three C₁₀₋₄₀ alkyl groups with a total of from 12to 100 carbons, and where the anion (a)(2) corresponds to Formula (II):

[M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II)

wherein:

M′ is a metal or metalloid selected from Groups 5-15 of the PeriodicTable of the Elements;

Q independently in each occurrence is selected from the group consistingof hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl,and substituted-hydrocarbyl radicals, including halo-substitutedhydrocarbyl radicals, and hydrocarbyl- and halohydrocarbyl-substitutedorgano-metalloid radicals, the hydrocarbyl portion in each of thesegroups preferably having from 1 to 20 carbons, with the proviso that innot more than one occurrence is Q halide; G is a polyvalent hydrocarbonradical having r+1 valencies bonded to M′ and r groups (T—H);

the group (T—H) is a radical wherein T comprises O, S, NR, or PR, the O,S, N or P atom of which is bonded to hydrogen atom H wherein R is ahydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical or hydrogen;

m is an integer from 1 to 7;

n is an integer from 0 to 7;

q is an integer of 0 or 1;

r is an integer from 1 to 3;

z is an integer from 1 to 8;

d is an integer from 1 to 7; and

n+z−m=d.

Surprisingly, it has been found that the ionic compound (a) can beadvantageously used in a solid form dispersed in a diluent in which (a)is insoluble or sparingly soluble (the diluent in which (a) is insolubleor sparingly soluble is also referred to as “nonsolvent”; the diluent inwhich (a) is soluble is also referred to as “solvent”). By use of thedispersed solid ionic compound (a) in association with transition metalcompound (b) and organometal compound (c) an active solid particulateaddition polymerization catalyst results, preferably in dispersed form.Such a solid dispersed catalyst advantageously can be used in a particleforming polymerization process, such as a slurry or gas phasepolymerization process, without requiring an additional support materialto produce polymer of the desired particle size and morphology. Thesolid dispersed catalysts of the present invention can produce polymersin the form of free flowing powder or particles, without causingsubstantial polymer deposits at reactor walls and other moving parts inthe reactors. Free flowing ethylene based polymers and interpolymerspreferably have bulk densities of at least about 0.20 g/cm³, and morepreferably of at least about 0.25 g/cm³.

In another aspect of this invention there is provided a compound whichis the reaction product of (a) an ionic compound described above and (c)an organometal or metalloid compound wherein the metal or metalloid isselected from the Groups 1-14 of the Periodic Table of the Elements. Adesirable embodiment is that where the compound corresponds to theformula

[L*—H]⁺[(C₆F₅)₃BC₆H₄—O—M^(o)R^(c) _(x−1)X^(a) _(y)]−,

wherein

M^(o) is a metal or metalloid selected from Groups 1-14 of the PeriodicTable of the Elements,

R^(c) independently each occurrence is hydrogen or a group having from 1to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, orhydrocarbylsilylhydrocarbyl;

X^(a) is a noninterfering group having from 1 to 100 nonhydrogen atomswhich is halo-substituted hydrocarbyl, hydrocarbylamino-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino,di(hydrocarbyl)amino, hydrocarbyloxy or halide;

x is a nonzero integer which may range from 1 to an integer equal to thevalence of M^(o);

y is zero or a nonzero integer which may range from 1 to an integerequal to 1 less than the valence of M^(o); and

x+y equals the valence of M^(o).

In a further aspect of this invention there is provided a substantiallyinactive catalyst precursor comprising (a) an ionic compound describedabove, and (b) a transition metal compound.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1A and FIG. 1B are scanning electron micrographs of slurry producedpolyethylene at a magnification of 50 times.

FIG. 2A and FIG. 2B are scanning electron micrographs of slurry producedpolyethylene at a magnification of 200 times.

FIG. 3A and FIG. 3B are scanning electron micrographs of slurry producedpolyethylene at a magnification of 1000 times.

DETAILED DESCRIPTION OF THE INVENTION

All references herein to elements or metals belonging to a certain Grouprefer to the Periodic Table of the Elements published and copyrighted byCRC Press, Inc., 1989. Also any reference to the Group or Groups shallbe to the Group or Groups as reflected in this Periodic Table of theElements using the IUPAC system for numbering groups.

The term “nonsupported” as used in the present application means in theabsence of a material which typically may be used as a support orcarrier in an addition polymerization catalyst, more in particular as anolefin addition polymerization catalyst. Conversely, the term“supported” as used in the present application means in the presence ofa material which typically may be used as a support or carrier in anaddition polymerization catalyst, more in particular as an olefinaddition polymerization catalyst. Where in the present application theterm “solid catalyst” is used, it embraces both nonsupported andsupported solid catalysts, unless it follows differently from thecontext.

Where in the present invention a composition is defined by its startingcomponents or starting compounds optionally in combination with certainprocess steps, such as for example contacting and combining steps, it ismeant that the composition encompasses starting components or startingcompounds but also the reaction product or reaction products of thestarting components or starting compounds to the extent a reaction hastaken place.

The dispersion of (a) of the present invention is preferablycharacterized by an average particle size of (a), as measured by laserdiffraction, in the range of from 0.1 to 200 μm, more preferably in therange of from 0.5 to 50 μm. The dispersion of (a) preferably containsfrom 0.00001 to 10 mole of solid compound (a)/l, more preferably from0.0001 to 1 mole/l. The particle size of the dispersion of (a) wasmeasured using a Malvern Mastersizer particle size analyzer.

Some ionic compounds (a) to be used in the present invention and theirmethods of preparation are described in U.S. patent application Ser. No.08/610,647, filed Mar. 4, 1996 (corresponding to WO-96/28480) which isincorporated herein by reference. Other ionic compounds are more nearlyrelated to those disclosed in U.S. patent application Ser. No., filed[42808A], some of which may be useful in various aspects of thisinvention. Preferred ionic compounds of this invention have notpreviously been disclosed, and have the advantage of being highlysoluble in the solvents and diluents used in various methods utilizingthese ionic compounds, while at the same time the preferred ioniccompounds contain a moiety having an active hydrogen. The term used inthe anion (a)(2) of the ionic compound “at least one substituentcomprising a moiety having an active hydrogen” means in the presentapplication a substituent comprising a hydrogen atom bonded to anoxygen, sulphur, nitrogen or phosphorous atom. The presence of at leastone moiety having an active hydrogen in the ionic compound imparts anunprecedented versatility to it in the catalyst arts, for it is capableof entering into various reactions primarily through covalent bonding,such as, for example, bonding to a tethering group, such as, forexample, a surface hydroxyl group of a support material, or in forming areaction product with an organometal or metalloid compound, or informing a complex or reaction product with a transition metal compound.

When various chemical formulas are used herein to represent variouschemical compounds, it should be recognized that the formula isemperical and not necessarily molecular. In particular, with regard tovarious organometal or metalloid compounds, especially those containingaluminum, and to the various alumoxanes, it is understood that a singleemperical formula may be used as is conventional in the catalyst arts torepresent what may be various dimers, trimers and other higheroligomers, depending upon the physical environment including varioussolvents or diluents in which the compound is employed.

The anion (a)(2) comprises a single Group 5-15 element or a plurality ofGroup 5-15 elements but is preferably a single coordination complexcomprising a charge-bearing metal or metalloid core. Preferred anions(a)(2) are those containing a single coordination complex comprising acharge-bearing metal or metalloid core carrying the at least onesubstituent containing a moiety having an active hydrogen. Suitablemetals for the anions of ionic compounds (a) include, but are notlimited to, aluminum, gold, platinum and the like. Suitable metalloidsinclude, but are not limited to elements of Groups 13, 14, and 15, ofthe Periodic Table of Elements, preferably are, boron, phosphorus, andsilicon. Ionic compounds which contain anions comprising a coordinationcomplex containing a single boron atom and one or more substituentscomprising a moiety having an active hydrogen are preferred. Examples ofsuitable anions comprising a single Group 5-15 element are disclosed inEP-277 004 and examples of those having a plurality of Group 5-15elements are disclosed in EP-0 277 003, with the proviso that at leastone of the subsituents in the anions described therein is substituted bya substituent comprising a moiety having an active hydrogen, preferablyG_(q) (T—H)_(r).

Preferably, anions (a)(2) may be represented by a single coordinationcomplex of the following general Formula (II):

[M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II)

wherein:

M′ is a metal or metalloid selected from Groups 5-15 of the PeriodicTable of the Elements;

Q independently in each occurrence is selected from the group consistingof hydride, dihydrocarbylamido, preferably dialkylamido, halide,hydrocarbyloxide, preferably alkoxide and aryloxide, hydrocarbyl, andsubstituted-hydrocarbyl radicals, including halo-substituted hydrocarbylradicals, and hydrocarbyl- and halohydrocarbyl-substitutedorgano-metalloid radicals, the hydrocarbyl portion in each of thesegroups preferably having from 1 to 20 carbons, with the proviso that innot more than one occurrence is Q halide;

G is a polyvalent hydrocarbon radical having r+1 valencies, andpreferably a divalent hydrocarbon radical, bonded to M′ and r groups(T—H);

the group (T—H) is a radical wherein T comprises O, S, NR, or PR, the O,S, N, or P atom of which is bonded to hydrogen atom H, wherein R is ahydrocarbon radical, a trihydrocarbyl silyl radical, a trihydrocarbylgermyl radical, or hydrogen;

m is an integer from 1 to 7, preferably 3;

n is an integer from 0 to 7, preferably 3;

q is an integer 0 or 1, preferably 1;

r is an integer from 1 to 3, preferably 1;

z is an integer from 1 to 8, preferably 1 or 2;

d is an integer from 1 to 7, preferably 1; and

n+z−m=d.

When q is 0 and polyvalent hydrocarbon radical G is not present, T isbound to M′. Preferred boron-containing anions (a)(2) which areparticularly useful in this invention may be represented by thefollowing general Formula (III):

 [BQ_(4−z′)(G_(q)(T—H)_(r))_(z′)]^(d−)  (III)

wherein:

B is boron in a valence state of 3;

z′ is an integer from 1-4, preferably 1 or 2, most preferably 1;

d is 1; and

Q, G, T, H, q, and r are as defined for Formula (II). Preferably, z′ is1 or 2, q is 1, and r is 1.

In the anion (a)(2), the at least one substituent comprising, a moietyhaving an active hydrogen preferably corresponds to Formula I:

G_(q)(T—H)_(r)  (I)

wherein G is a polyvalent hydrocarbon radical, the group (T—H) is aradical wherein T comprises O, S, NR, or PR, the O, S, N, or P atom ofwhich is bonded to hydrogen atom H, wherein R is a hydrocarbyl radical,a trihydrocarbyl silyl radical, a trihydrocarbyl germyl radical, orhydrogen, H is hydrogen, q is 0 or 1, and preferably 1, and r is aninteger from 1 to 3, preferably 1. Polyvalent hydrocarbon radical G hasr+1 valencies, one valency being associated with a metal or metalloid ofthe Groups 5-15 of the Periodic Table of the Elements in the anion, theother r valencies of G being attached to r groups (T—H). Preferredexamples of G include di- or trivalent hydrocarbon radicals such as:alkylene, arylene, aralkylene, or alkarylene radicals containing from 1to 20 carbon atoms, more preferably from 2 to 12 carbon atoms. Suitableexamples of divalent hydrocarbon radicals G include phenylene,biphenylene, naphthylene, methylene, ethylene, 1,3-propylene,1,4-butylene, phenylmethylene (—C₆H₄—CH₂—). The polyvalent hydrocarbylportion G may be further substituted with radicals that do notnegatively impact the effect to be achieved by the present invention.Preferred examples of such noninterfering substituents are alkyl, aryl,alkyl- or aryl-substituted silyl and germyl radicals, and fluorosubstituents.

The group (T—H) in the previous formula may be an —OH, —SH, —NRH, or—PRH group, wherein R preferably is a C₁₋₁₈, preferably a C₁₋₁₂,hydrocarbyl radical or hydrogen, and H is hydrogen. Preferred R groupsare alkyls, cycloalkyls, aryls, arylalkyls, or alkylaryls of 1 to 18carbon atoms, more preferably those of 1 to 12 carbon atoms.Alternatively, the group (T—H) comprises an —OH, —SH, —NRH, or —PRHgroup which are part of a larger functional moiety such as, for example,C(O)—OH, C(S)—OH, C(S)—SH, C(O)—SH, C(O)—NRH, C(S)—NRH, and C(O)—PRH,and C(S)—PRH. Most preferably, the group (T—H) is a hydroxy group, —OH,or an amino group, —NRH.

Very preferred substituents G_(q)(T—H) in anion (a)(2) include hydroxy-and amino-substituted aryl, aralkyl, alkaryl or alkyl groups, and mostpreferred are the hydroxyphenyls, especially the 3- and 4-hydroxyphenylgroups and 2,4-dihydroxyphenyl, hydroxytolyls, hydroxybenzyls(hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyls,hydroxycyclohexyls, hydroxymethyls, and hydroxypropyls, and thecorresponding amino-substituted groups, especially those substitutedwith —NRH wherein R is an alkyl or aryl radical having from 1 to 10carbon atoms, such as for example methyl, ethyl, propyl, i-propyl, n-,i-, or t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, phenyl,benzyl, tolyl, xylyl, naphthyl, and biphenyl.

Illustrative, but not limiting, examples of anions (a)(2) of ioniccompounds to be used in the present invention are boron-containinganions such as:

triphenyl(hydroxyphenyl)borate, triphenyl(2,4-dihydroxyphenyl)borate,

tri(p-tolyl )(hydroxyphenyl )borate,

tris-(pentafluorophenyl )(hydroxyphenyl )borate,tris-(2,4-dimethylphenyl)(hydroxyphenyl)borate,

tris-(3,5-dimethylphenyl)(hydroxyphenyl)borate,

tris-(3,5-di-trifluoromethyl-phenyl)(hydroxyphenyl)borate,tris(pentafluorophenyl)(2-hydroxyethyl)borate,tris(pentafluorophenyl)(4-hydroxybutyl)borate,

tris(pentafluorophenyl)(4-hydroxycyclohexyl)borate,tris(pentafluorophenyl)(4-(4′-hydroxyphenyl)phenyl)borate,tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate,

and the like.

Further preferred anions (a)(2) include those containing twosubstituents containing a moiety having an active hydrogen, for example:diphenyldi(hydroxyphenyl)borate, diphenyldi(2,4-dihydroxyphenyl)borate,di(p-tolyl)di(hydroxyphenyl)borate,di(pentafluorophenyl)di-(hydroxyphenyl)borate, di(2,4-dimethylphenyl)di(hydroxyphenyl)borate, di(3,5-dimethylphenyl)di(hydroxyphenyl)borate,di(3,5-di-trifluoromethylphenyl)di(hydroxyphenyl)borate,di(pentafluorophenyl)di(2-hydroxyethyl)borate,di(pentafluorophenyl)di(4-hydroxybutyl)borate,di(pentafluorophenyl)di(4-hydroxycyclohexyl)borate,di(pentafluorophenyl)di(4-(4′-hydroxyphenyl)phenyl)borate,di(pentafluorophenyl)di(6-hydroxy-2-naphthyl)borate, and the like.

Other preferred anions are those above-mentioned borates wherein thehydroxy functionality is replaced by an amino NHR functionality whereinR preferably is methyl, ethyl, or t-butyl. A highly preferred anion(a)(2) is tris(pentafluorophenyl)(4-hydroxyphenyl)borate.

The cationic portion (a)(1) of the ionic compound is preferably selectedfrom the group consisting of Bronsted acidic cations, especiallyammonium and phosphonium cations or sulfonium cations, carboniumcations, silylium cations, oxonium cations, organometallic cations andcationic oxidizing agents. The cations (a)(1) and the anions (a)(2) areused in such ratios as to give a neutral ionic compound.

Bronsted acidic cations may be represented by the following generalformula:

(L—H)⁺

wherein:

L is a neutral Lewis base, preferably a nitrogen, phosphorus, oxygen, orsulfur containing Lewis base; and (L—H)⁺ is a Bronsted acid.

Illustrative, but not limiting, examples of Bronsted acidic cations aretrihydrocarbyl- and preferably trialkyl-substituted ammonium cationssuch as

triethylammonium, tripropylammonium, tri(n-butyl)ammonium,trimethylammonium,

tri(i-butyl)ammonium, and tri(n-octyl)ammonium. Also suitable areN,N-dialkyl anilinium cations such as N,N-dimethylanilinium,N,N-diethyl-anilinium, N,N-2,4,6-pentamethylanilinium,

N,N-dimethylbenzylammonium and the like; dialkylammonium cations such asdi-(i-propyl)ammonium, dicyclohexylammonium and the like; andtriarylphosphonium cations such as triphenylphosphonium,tri(methylphenyl)phosphonium,

tri(dimethylphenyl)phosphonium, dimethylsulphonium, diethylsulphonium,and diphenylsulphonium.

In a highly preferred embodiment, the Bronsted acidic cation (a)(1) maybe represented by the following general formula:

[L*—H]⁺,

wherein:

L* is a nitrogen, oxygen, sulfur or phosphorus containing Lewis basewhich comprises at least one relatively long chain alkyl group.Preferably such L* groups contain from one to three C₁₀₋₄₀ alkyl groupswith a total of from 12 to 100 carbons, more preferably two C₁₀₋₄₀ alkylgroups and from 21 to 90 total carbons. It is understood that the cationmay comprise a mixture of alkyl groups of differing lengths. Forexample, one suitable cation is the protonated ammonium salt derivedfrom the commercially available long chain amine comprising a mixture oftwo C₁₄, C₁₆ or C₁₈ alkyl groups and one methyl group. Such amines areavailable from Witco Corp., under the trade name Kemamine™ T9701, andfrom Akzo-Nobel under the trade name Armeen™ M2HT. These preferredcations are described in U.S. provisional application Ser. No.60/014284, filed Mar. 27, 1996, which is incorporated herein byreference. Ionic compounds (a) comprising the cation [L*—H]⁺ can beeasily prepared by subjecting an ionic compound comprising the cation[L—H]⁺ and the anion (a)(2), as prepared in U.S. patent application Ser.No. 08/610,647, filed Mar. 4, 1996 (corresponding to WO-96/28480), to acation exchange reaction with a [L*—H]⁺ salt.

Generally, the preferred ionic compounds have a solubility in toluene at22° C. of at least 0.1 weight percent, desirably, of at least 0.3 weightpercent, more desirably of at least 1 weight percent, preferably of atleast 5 weight percent, more preferably of at least 10 weight percentand in some instances even more than 15 weight percent.

Illustrative, but not limiting examples of the highly preferred cations(a)(1) are

tri-substituted ammonium salts such as: decyldi(methyl)ammonium,

dodecyldi(methyl)ammonium, tetradecyldi(methyl)ammonium,

hexaadecyldi(methyl)ammonium, octadecyldi(methyl)ammonium,

eicosyldi(methyl)ammonium, methyldi(decyl)ammonium,

methyldi(dodecyl)ammonium, methyldi(tetradecyl)ammonium,

methyldi(hexadecyl)ammonium, methyldi(octadecyl)ammonium,

methyldi(eicosyl)ammonium, tridecylammonium, tridodecylammonium,

tritetradecylammonium, trihexadecylammonium, trioctadecylammonium,

trieicosylammonium, decyldi(n-butyl)ammonium,dodecyldi(n-butyl)ammonium,

octadecyldi(n-butyl)ammonium,

N,N-didodecylanilinium, N-methyl-N-dodecylanilinium,

N,N-di(octadecyl)(2,4,6-trimethylanilinium),cyclohexyldi(dodecyl)ammonium, and methyldi(dodecyl)ammonium.

Suitable similarly substituted sulfonium or phosphonium cations such as,di(decyl)sulfonium, (n-butyl)dodecylsulfonium, tridecylphosphonium,di(octadecyl)methylphosphonium, and tri(tetradecyl)phosphonium, may alsobe named.

Preferred ionic compounds (b) are di(octadecyl)methylammoniumtris(pentafluorophenyl)(hydroxyphenyl)borate, octadecyl dimethylammoniumtris(pentafluorophenyl)borate and di(octadecyl)(n-butyl)ammoniumtris(pentafluorophenyl)(hydroxyphenyl)-borate, as well as the amino(—NHR) analogues of these compounds wherein the hydroxyphenyl group isreplaced by the aminophenyl group.

A second type of suitable cation corresponds to the formula: (Ĉ⁺,wherein Ĉ⁺ is a stable carbonium or silylium ion containing up to30(nonhydrogen atoms. Suitable examples of cations include tropyllium,triphenylmethylium, benzene(diazonium). Silylium salts have beenpreviously generically disclosed in J. Chem. Soc. Chem. Comm., 1993,383-384, as well as Lambert, J. B., et. al., Organometallics, 1994, 13,2430-2443. Preferred silylium cations are triethylsilylium, andtrimethylsilylium and ether substituted adducts thereof.

Another suitable type of cation comprises a cationic oxidizing agentrepresented by the formula:

 Ox ^(e+)

wherein Ox^(e+) is a cationic oxidizing agent having a charge of e+, ande is an integer from 1 to 3.

Another suitable type of cation comprises an organometallic cation, suchas, for example, AlR^(t) ₂ ⁺, where R^(t) is a hydrocarbyl orsubstituted hydrocarbyl having from 1 to 100 nonhydrogen atoms, orS-AlR^(t+), where S is a support material or other substrate havingtethered to it an AlR^(t+) group, where R^(t) is as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, and Pb²⁺.

According to a further aspect of the present invention there is provideda nonsupported catalyst comprising the ionic compound (a), (b) atransition metal compound, and (c) an organometal compound wherein themetal is selected from the Groups 1-14 of the Periodic Table of theElements. The nonsupported catalyst may be formed from solublecomponents (a), (b) and (c) and used in a diluent in which it issoluble, such as, for example, in a solution polymerization process, orit may be recovered as a solid in dry particulate form. In one aspect ofthis invention, the nonsupported solid catalysts are preferablydispersed in a diluent in which the solid catalyst is insoluble orsparingly soluble.

The present invention furthermore provides a supported solid catalystcomprising ionic compound (a), transition metal compound (b),organometal compound (c), and a support material (d). Suitable ioniccompounds (a) have been described hereinabove.

Suitable transition metal compounds (b) for use in the present inventioninclude any compound or complex of a metal of Groups 3-10 of thePeriodic Table of the Elements capable of being activated to olefininsertion and polymerization when combined with components (a) and (c)and optionally (d) of the present invention. Examples include Group 10transition metal diimine derivatives which are described in WO-96/23010.

Additional catalysts include derivatives of Group 3, 4, 5, or 6 orLanthande metals which are in the +2, +3, or +4 formal oxidation state.Preferred compounds include metal complexes containing from 1 to 3π-bonded anionic or neutral ligand groups, which may be cyclic ornoncyclic delocalized π-bonded ligand groups. Exemplary of such π-bondedligand groups are conjugated or nonconjugated, cyclic or noncyclicdienyl groups, allyl groups, boratabenzene groups, and arene groups. Bythe term “π-bonded” is meant that the ligand group is bonded to thetransition metal by means of delocalized π electrons thereof.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl substitutedmetalloids, hydrocarbyloxy, dihydrocarbylamino, wherein the metalloid isselected from Group 14 of the Periodic Table of the Elements andhydrocarbyl radicals or hydrocarbyl-substituted metalloid radicalsfurther substituted with a Group 15 or 16 heteroatom containing moiety.Included within the term “hydrocarbyl” are C₁₋₂₀ straight, branched andcyclic alkyl radicals, C₆₋₂₀ aromatic radicals, C₇₋₂₀ alkyl-substitutedaromatic radicals, and C₇₋₂₀ aryl-substituted alkyl radicals. Inaddition two or more such radicals may together form a fused ringsystem, a hydrogenated fused ring system, or a metallocycle with themetal. Suitable hydrocarbyl-substituted organometalloid radicals includemono-, di- and tri-substituted organometalloid radicals of Group 14elements wherein each of the hydrocarbyl groups contains from 1 to 20carbon atoms. Examples of suitable hydrocarbyl-substitutedorganometalloid radicals include trimethylsilyl, triethylsilyl,ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, andtrimethylgermyl groups. Such hydrocarbyl and hydrocarbyl-substitutedorganometalloid radicals may be further substituted with a Group 15 or16 heteroatom containing moiety. Examples of Group 15 or 16 heteroatomcontaining moieties include amine, phosphine, ether or thioethermoieties (see for example the compounds disclosed in WO-96/13529) ordivalent derivatives thereof, for example amide, phosphide, ether orthioether groups bonded to the transition metal or Lanthande metal, andbonded to the hydrocarbyl group or to the hydrocarbyl substitutedmetalloid containing group.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,and boratabenzene groups, as well as C₁₋₁₀ hydrocarbyl-substituted,C₁₋₁₀ hydrocarbyl-substituted silyl substituted, C₁₋₁₀ hydrocarbylsubstituted germyl derivatives thereof, and divalent derivatives of theforegoing substituents. Preferred anionic delocalized π-bonded groupsare cyclopentadienyl, pentamethylcyclopentadienyl,tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl,2,3-dimethylindenyl, fluorenyl, 2-methylindenyl,2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, andtetrahydroindenyl.

The boratabenzenes are anionic ligands which are boron containinganalogues to benzene. They are previously known in the art having beendescribed by G. Heirberich, et al., in Organometallics, 14,1, 471-480(1995). Preferred boratabenzenes correspond to the formula:

wherein R″ is selected from the group consisting of hydrocarbyl, silyl,or germyl, said R″ having up to 20 nonhydrogen atoms.

A suitable class of transition metal compounds useful in the presentinvention corresponds to the formula (V):

L_(l)MX_(m)X′_(n)X″_(p), or a dimer thereof  (V)

wherein:

L is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 nonhydrogen atoms, optionally two L groups may bejoined together forming a bridged structure, and further optionally oneL may be bound to X;

M is a metal of Group 4 of the Periodic Table of the Elements in the +2,+3 or +4 formal oxidation state;

X is an optional, divalent substituent of up to 50 nonhydrogen atomsthat together with L forms a metallocycle with M;

X′ is an optional neutral ligand base having up to 20 nonhydrogen atoms:

X″ each occurrence is a monovalent, anionic moiety having up to 40nonhydrogen atoms, optionally, two X″ groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or, optionally two X″ groups may be covalently bound together toform a neutral, conjugated or nonconjugated diene that is π-bonded to M,or further optionally one or more X″ and one or more X′ groups may bebonded together thereby forming a moiety that is both covalently boundto M and coordinated thereto by means of Lewis base functionality;

l is 0, 1 or 2;

m is 0 or 1;

n is a number from 0 to 3;

p is an integer from 0 to 3; and

the sum, l+m+p, is equal to the formal oxidation state of M, except whentwo X″ groups together form a neutral conjugated or nonconjugated dienethat is π-bonded to M, in which case the sum l+m is equal to the formaloxidation state of M.

Preferred complexes include those containing either one or two L groups.The latter complexes include those containing a bridging group linkingthe two L groups. Preferred bridging groups are those corresponding tothe formula (ER*₂)_(x) wherein E is silicon, germanium, tin, or carbon,R* independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R*having up to 30 carbon or silicon atoms, and x is 1 to 8. Preferably, R*independently each occurrence is methyl, ethyl, propyl, benzyl,tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two L groups are compoundscorresponding to the formula (VI) and (VII):

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having tip to 20 nonhydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

X″ independently each occurrence is an anionic ligand group of up to 40nonhydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 nonhydrogen atoms or together are a conjugateddiene having from 4 to 30 nonhydrogen atoms forming a π-complex with M,whereupon M is in the +2 formal oxidation state, and

R*, E and x are as previously defined for bridging groups (ER*₂)_(x).

The foregoing metal complexes are especially suited for the preparationof polymers having stereoregular molecular structure. In such capacityit is preferred that the complex possesses C_(s) symmetry or possesses achiral, stereorigid structure. Examples of the first type are compoundspossessing different delocalized π-bonded systems, such as onecyclopentadienyl group and one fluorenyl group. Similar systems based onTi(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefinpolymers in Ewen, et al., J. Am. Chem. Soc. 100, 6255-6256 (1980).Examples of chiral structures include rac bis-indenyl complexes. Similarsystems based on Ti(IV) or Zr(IV) were disclosed for preparation ofisotactic olefin polymers in Wild et al., J. Organomet. Chem., 232,233-47, (1982).

Exemplary bridged ligands containing two π-bonded groups are:(dimethylsilyl-bis(cyclopentadienyl)),(dimethylsilyl-bis(methlcyclopentadienyl)),(dimethylsilyl-bis(ethylcyclopentadineyl)),(dimethylsilyl-bis)t-butylcyclopentadineyl)),(dimethylsilyl-bis(tetramethylcyclopentadienyl)),(dimethylsilyl-bis)indenyl)), dimethylsilyl-bis(tetrahydroindenyl)),dimethylsilyl-bis(fluorenyl)), dimethylsilyl-bis(tetrahydrofluorenyl)),dimethylsilyl-bis(2-methyl-4-phenylindenyl)),(dimethylsilyl-bis(2-methylindenyl)),dimethylsilylcyclopentadienyl-fluorenyl),(dimethylsilyl-cyclopentadienyl-octahydrofluorenyl),(dimethylsilyl-cyclopentadienyl-tetrahydrofluorenyl),(1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl),(1,2-bis(cyclopentadienyl)ethane, and(isopropylidenecyclopentadienyl-fluorenyl).

Preferred X″ groups in formula (VI) and (VII) are selected from hydride,hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyland aminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

A further class of metal complexes utilized in the present inventioncorresponds to the preceding formula (V)L₁MX_(m)X′_(n)X″_(p), or a dimerthereof, wherein X is a divalent substituent of up to 50 nonhydrogenatoms that together with L forms a metallocycle with M.

Preferred divalent X substituents include groups containing up to 30nonhydrogen atoms comprising at least one atom that is oxygen, sulfur,boron or a member of Group 14 of the Periodic Table of the Elementsdirectly attached to the delocalized π-bonded group, and a differentatom, selected from the group consisting of nitrogens phosphorus, oxygenor sulfur that is covalently bonded to M.

A preferred class of such Group 4 metal coordination complexes usedaccording to the present invention corresponds to the formula (VIII):

wherein:

M is titanium or zirconium, preferably titanium in the +2, +3, or +4formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo,hydrocarbyloxy, dihydrocarbylamino, and combinations thereof, said R³having up to 20 nonhydrogen atoms, or adjacent R³ groups together form adivalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiylgroup) thereby forming a fused ring system;

each X″ in formula (VIII) is a hydride, halide, hydrocarbyl,hydrocarbyloxy or silyl group, said group having up to 20 nonhydrogenatoms, or two X″ groups together form a neutral C₅₋₃₀ conjugated dieneor a divalent derivative thereof;

Y is —O—, —S—, —NR*—, —PR*—, —NR*₂ or —PR*₂; and

Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, or GeR*₂,wherein R* is as previously defined.

According to the present invention there are provided metal complexescorresponding to the formula I:

where M is titanium, zirconium or hafnium in the +2, +3 or +4 formaloxidation state;

R′ is an aryl ligand or a halo-, silyl-, alkyl-, cycloalkyl-,dihydrocarbylamino-, hydrocarbyloxy-, or hydrocarbyleneamino-,substituted derivative thereof, said R′ having, from 6 to 40 nonhydrogenatoms;

Z is a divalent moiety, or a moiety comprising one σ-bond and a neutraltwo electron pair able to form a coordinate-covalent bond to M, said Zcomprising, boron, or a member of Group 14 of the Periodic Table of theElements, and also comprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups;

X′ independently each occurrence is a neutral Lewis base ligatingcompound having up to 20 atoms;

X″ is a divalent anionic ligand group having up to 60 atoms;

p is zero, 1, 2, or 3;

q is zero, 1 or 2; and

r is zero or 1.

Another class of preferred metal complexes for use in the presentinvention corresponding to the formula:

where M is a metal from one of Groups 3 to 13 of the Periodic Table ofthe Elements, the lanthanides or actinides, which is in the +2, +3 or +4formal oxidation state and which is π-bonded to one cyclopentadienylgroup (Cp) which is a cyclic, delocalized, π-bound ligand group having 5substituents: R^(A); (R^(B))_(j)—T where j is zero, 1 or 2; R^(C); R^(D)and Z; where R^(A), R^(B), R^(C) and R^(D) are R groups; and where

T is a heteroatom which is covalently bonded to the Cp ring, and toR^(B) when j is 1 or 2, and when j is 0, T is F, Cl, Br, or I; when j is1, T is O or S, or N or P and R^(B) has a double bond to T; when j is 2,T is N or P; and where

R^(B) independently each occurrence is hydrogen, or, is a group havingfrom 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyhydrocarbyl,hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, each R^(B)optionally being substituted with one or more groups which independentlyeach occurrence is hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino,di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido,hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylor hydrocarbylsilyhydrocarbyl having from 1 to 20 nonhydrogen atoms, ora noninterfering group having from 1 to 20 nonhydrogen atoms; and eachof R^(A), R^(C) and R^(D) is hydrogen, or is a group having from 1 to 80nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl,hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substitutedhydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each R^(A),R^(C) or R^(D) optionally being substituted with one or more groupswhich independently each occurrence is hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino,hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl,hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substitutedhydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylihydrocarbyl havingfrom 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1to 20 nonhydrogen atoms: or, optionally, two or more of R^(A), R^(B),R^(C) and R^(D) are covalently linked with each other to form one ormore fused rings or ring systems having from 1 to 80 nonhydrogen atomsfor each R group, the one or more fused rings or ring systems beingunsubstituted or substituted with one or more groups which independentlyeach occurrence are hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino,di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido,hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylor hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, ora noninterfering group having from 1 to 20 nonhydrogen atoms;

Z is a divalent moiety bound to both Cp and M via σ-bonds, where Zcomprises boron, or a member of Group 14 of the Periodic Table of theElements, and also comprises nitrogen, phosphorus, sulfur or oxygen;

X is an anionic or dianionic ligand group having up to 60 atomsexclusive of the class of ligands that are cyclic, delocalized, π-boundligand groups;

X′ independently each occurrence is a neutral Lewis base ligatingcompound having up to 20 atoms;

p is zero, 1 or 2, and is two less than the formal oxidation state of M,when X is an anionic ligand; when X is a dianionic ligand group, p is 1;and

q is zero, 1 or 2.

Another class of preferred metal complexes for use in the presentinvention corresponding to the formula:

where M is a metal from one of Groups is 3 to 13 of the Periodic Tableof the Elements, the lanthanides or actinides, which is in the +2, +3 or+4 formal oxidation state and which is π-bonded to one cyclopentadienylgroup (Cp) which is a cyclic, delocalized, π-bound ligand group having 5substituents: (R^(A))_(j)—T where j is zero, 1 or 2, where R^(A), R^(B),R^(C) and R^(D) are R groups: and where

T is a heteroatom which is covalently bonded to the Cp ring, and toR^(A) when j is 1 or 2, and when j is 0, T is F, Cl, Br, or I; when j is1, T is O or S, or N or P and R^(A) has a double bond to T; when j is 2,T is N or P; and where

R^(A) independently each occurrence is hydrogen, or, is a group havingfrom 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl,hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, each R^(A)optionally being, substituted with one or more groups whichindependently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino,di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido,hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylor hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, ora noninterfering, group having from 1 to 20 nonhydrogen atoms; and eachof R^(B), R^(C) and R^(D) is hydrogen, or is a group having from 1 to 80nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl,hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substitutedhydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each R^(B),R^(C) or R^(D) optionally being substituted with one or more groupswhich independently each occurrence is hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino,hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl,hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substitutedhydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20nonhydrogen atoms; or, optionally, two or more of R^(A), R^(B), R^(C)and R^(D) are covalently linked with each other to form one or morefused rings or ring systems having from 1 to 80 nonhydrogen atoms foreach R group, the one or more fused rings or ring systems beingunsubstituted or substituted with one or more groups which independentlyeach occurrence are hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino,di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbylsulfido,hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylor hydrocarbylsilylhydrocarbyl having, from 1 to 20 nonhydrogen atoms,or a noninterfering group having from 1 to 20) nonhydrogen atoms;

Z is a divalent moiety bound to both Cp and M via σ-bonds, where Zcomprises boron, or a member of Group 14 of the Periodic Table of theElements, and also comprises nitrogen, phosphorus, sulfur or oxygen;

X is an anionic or dianionic ligand group having up to 60 atomsexclusive of the class of ligands that are cyclic, delocalized, π-boundligand groups;

X′ independently each occurrence is a neutral Lewis base ligatingcompound having up to 20 atoms;

p is zero, 1 or 2, and is two less than the formal oxidation state of M,when X is an anionic ligand; when X is a dianionic ligand group, p is 1;and

q is zero, 1 or 2.

Specific examples of some of the transition metal compounds of the typesdescribed above can be found in EP-0 129 368; EP-0 277 004; EP-0 416815; WO-93/19104; WO-95/00526; WO-96/00734; WO-96/04290; WO-96/08498;while others, especially constrained geometry metal complexes andmethods for their preparation, are disclosed in U.S. application Ser.No. 545,403, filed Jul. 3, 1990; U.S. application Ser. No. 547,718,filed Jul. 3, 1990 ABN (EP-A-468,651); U.S. application Ser. No.702,475, filed May 20, 1991 ABN (EP-A-514,828); U.S. application Ser.No. 876,268, filed May 1, 1992, U.S. Pat. No. 5,721,185 (EP-A-520,732);and U.S. application Ser. No. 8.003, filed Jan. 21, 1993 U.S. Pat. No.5,374,696); as well as U.S. Pat. Nos. 5,055,438; 5,057,475; 5,096,867;5,064,802; 5,132,380; WO-96/28480; WO-97/15583; U.S. application Ser.No. 08/689,163 filed Aug. 7, 1996 ABN; U.S. application Ser. No.08/818,530 filed Mar. 14, 1997 U.S. Pat. No. 5,919,983; WO-97/35893:U.S. application Ser. No. 60/017,147 filed May 17, 1996; PCT ApplicationNo. PCT/US97/08206 filed May 16, 1997; PCT Application No.PCT/US97/08466 filed May 16, 1997; U.S. application Ser. No. 60/034,819filed Dec. 19, 1996; U.S. application Ser. No. 60/023,768 filed Aug. 8,1996; PCT Application No. PCT/US97/13170 filed Jul. 28, 1997; PCTApplication No. PCT/US97/13171 filed Jul. 28, 1997; and U.S. applicationSer. No. 08/768,518 filed Dec. 18, 1996 U.S. Pat. No. 5,783,512. Also tobe found therein are teachings related to various olefin polymerizationprocesses and the products produced in those processes which arerelevant to the processes described herein for the use of variousaspects of this invention. The teachings of all of the foregoing patentsand the corresponding U.S., EP, and WO patent applications are herebyincorporated by reference.

Suitable organometal or metalloid compounds (c) for use in the presentinvention are those comprising a metal or metalloid of Groups 1-14. Inone aspect component (c) contains at least one substituent selected fromhydride, hydrocarbyl groups, trihydrocarbyl silyl groups, andtrihydrocarbyl germyl groups. It is desirable that this at least onesubstituent be capable of reacting with the moiety having all activehydrogen of the anion (a)(2)of the ionic compound. Additionalsubstituents preferably comprise one or more substituents selected fromhydride, halide, hydrocarbyloxide, dihydrocarbylamide hydrocarbylgroups, trihydrocarbyl substituted silyl groups, trihydiocarbylsubstituted germyl groups, and hydrocarbyl-, trihydrocarbyl silyl- ortrihydrocarbyl germyl-substituted metalloid groups. Desirableorganometal or metalloid compound (c) corresponds to the formula:

M^(o)R^(C) _(x)X^(a) _(y),

wherein M^(o) is a metal or metalloid selected from Groups 1-14 of thePeriodic Table of the Elements,

R^(C) independently each occurrence is hydrogen or a group having from 1to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl,trihydrocarbylsilyl, trihydrocarbylgermyl orhydrocarbylsilylhydrocarbyl;

X^(a) is a noninterfering group having from 1 to 100 nonhydrogen atomswhich is halo-substituted hydrocarbyl, hydrocarbylamino-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino,di(hydrocarbyl)amino, hydrocarbyloxy or halide;

x is a nonzero integer which may range from 1 to an integer equal to thevalence of M^(o);

y is zero or a nonzero integer which may range from 1 to an integerequal to 1 less than the valence of M^(o); and

x+y equals the valence of M^(o).

Preferred organometal compounds (c) are those where M^(o) is selectedfrom Groups 2, 12, 13 or 14 of the Periodic Table of Elements,moredesirably, Mg, Zn, B, Al, Ga, Si, Ge, Sn, or Pb, with aluminum andmagnesium being preferred and aluminum being the most preferred.

Examples of organometal compounds (c) include organolithium,organosodium, organomagnesium, organoscandium, organotitanium,organovanadium, organochromium, organomaganese, organoiron,organocobalt, organonickel, organocopper, organosilver, organozinc,organoboron, organoaluminum, organosilicon, organogermanium, organotin,and organolead compounds, and mixtures thereof.

Examples of preferred organometal compounds (c) include organlithium,organomagnesium, organozinc, organoboron, organoaluminum, organosilicon,organogermanium, organotin, and organolead compounds, mixtures thereof.More preferred examples are compounds represented by the followingformulae: MgR¹ ₂, ZnR¹ ₂, BR¹ _(x)R² _(y), AlR¹ _(x)R² _(y), wherein R¹independently each occurrence is hydride, a hydrocarbyl radical, atrihydrocarbyl silyl radical, a trihydrocarbyl germyl radical, or atrihydrocarbyl-, trihydrocarbyl silyl- or trihydrocarbylgermyl-substituted metalloid radical, R² independently is the same asR¹, x is 2 or 3, y is 0 or 1 and the sum of x and y is 3, and mixturesthereof. Examples of suitable hydrocarbyl moieties are those having from1 to 20 carbon atoms in the hydrocarbyl portion thereof, such as alkyl,aryl, alkaryl, or aralkyl. Preferred radicals include methyl, ethyl, n-or i-propyl. n-, s- or t-butyl, phenyl, and benzyl. Preferred components(c) are the aluminum and magnesium compounds, and especially thealuminum compounds. Preferably, the aluminum component is an aluminumcompounds of the formula AlR¹ _(x) wherein R¹ in each occurrenceindependently is hydride or a hydrocarbyl radical having from 1 to 20carbon atoms, and x is 3. Suitable trihydrocarbyl aluminum compounds aretrialkyl or triaryl aluminum compounds wherein each alkyl or aryl grouphas from 1 to 10 carbon atoms, or mixtures thereof, and preferablytrialkyl aluminum compounds such as trimethyl, triethyl, tri-isobutylaluminum.

Alumoxanes (also referred to as aluminoxanes) may also be used ascomponent (c), or (c) may be a mixture of one of the compounds mentionedin the preceding paragraphs and an alumoxane. Alumoxanes are oligomericor polymeric aluminum oxy compounds containing chains of alternatingaluminum and oxygen atoms, whereby the aluminum carries a substituent,preferably an alkyl croup. The structure of alumoxane is believed to berepresented by the following general formulae (—Al(R)—O)_(m), for acyclic alumoxane, and R₂Al—O(—Al(R)—O)_(m)—AlR₂, for a linear compoundswherein R independently in each occurrence is a C₁-C₁₀hydrocabyl,preferably alkyl, or halide and m is an integer ranging from1 to about 50, preferably at least about 4. Alumoxanes are typically thereaction products of water and an aluminum alkyl, which in addition toan alkyl group may contain halide or alkoxide groups. Reacting severaldifferent aluminum alkyl compounds, such as, for example, trimethylaluminum and tri-isobutyl aluminum, with water yields so-called modifiedor mixed alumoxanes. Preferred alumoxanes are methylalumoxane andmethylalumoxane modified with minor amounts of other lower alkyl groupssuch as isobutyl, Alumoxanes generally contain minor to substantialamounts of starting aluminum alkyl compound.

The way in which the alumoxane is prepared is not critical. Whenprepared by the reaction between water and aluminum alkyl, the water maybe combined with the aluminum alkyl in various forms, Such as liquid,vapor, of solid, for example in the form of crystallization water.Particular techniques for the preparation of alumoxane type compounds bycontacting an aluminum alkyl compound with an inorganic salt containing,water of crystallization are disclosed in U.S. Pat. No. 4,542,199. In aparticular preferred embodiment an aluminum alkyl compound is contactedwith a regeneratable water-containing substance such as hydratedalumina, silica or1 other substance. This is disclosed in EuropeanPatent Application No. 338,044.

According to a further aspect the invention provides a supported solidcatalyst comprising, (a), (b), and (c) as described hereinbefore, aswell as (d) a support material.

Suitable support materials (d), also referred to as carriers or carriermaterials, which may optionally be used in the present invention includethose support materials which are typically used in the art of supportedcatalysts, and more in particular the art of supported olefin additionpolymerization supported catalysts. Examples include porous resinousmaterials, for example, polyolefins such as polyethylenes andpolypropylenes or copolymers of styrene-divinylbenzene, and solidinorganic oxides including oxides of Group 2, 3, 4, 13, or 14 metals,such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide,as well as mixed oxides of silica. Suitable mixed oxides of silicainclude those of silica and one or more Group 2 or 13 metal oxides, suchas silica-magnesia or silica-alumina mixed oxides. Silica, alumina, andmixed oxides of silica and one or more Group 2 or, 13 metal oxides arepreferred support materials. Preferred examples of such mixed oxides arethe silica-aluminas. The most preferred support material is silica. Theshape of the silica particles is not critical and the silica may be ingranular, spherical, agglomerated, fumed or other form.

Support materials suitable for the present invention preferably have asurface area as determined by nitrogen porosimetry using the B.E.T.method from 10 to about 1000 m²/g, and preferably from about 100 to 600m²/g. The pore volume of the support, as determined by nitrogenadsorption, is typically up to 5 cm³/g, advantageously between 0.1 and 3cm³/g, preferably from about 0.2 to 2 cm³/g. The average particle sizeis not critical but typically is from 0.5 to 500 μm, preferably from 1to 200 μm, more preferably to 100 μm.

Preferred supports for use in the present invention include highlyporous silicas, aluminas, aluminosilicates, and mixtures thereof. Themost preferred support material is silica. The support material may bein granular. agglomerated, pelletized, or any other physical form.Suitable materials include, but are not limited to, silicas availablefrom Grace Davison (division of W. R. Grace & Co.) under thedesignations SD 3216.30, Davison Syloid™245, Davison 948 and Davison952, and from Crosfield under the designation ES70, and from Degussa AGunder the designation Acrosil™812; and aluminas available from AkzoChemicals Inc. under the designation Ketzen™ Grade B.

The support material may be subjected to a heat treatment and/orchemical treatment to reduce the water content or the hydroxyl contentof the support material. Both dehydrated support materials and supportmaterials containing small amounts of water can be used. Typical,chemical dehydration or dehydroxylation agents are reactive metalhydrides, alkyls and halides such as aluminum alkyls, alkyl siliconhalides and the like. Prior to its use, the support material can besubjected to a thermal treatment at 100° C. to 1000° C., preferably atabout 200° C. to about 850° C. in an inert atmosphere or under reducedpressure. Typically, this treatment is carried out for about 10 minutesto about 72 hours, preferably from about 0.5 hours to 24 hours.

The support material. optionally thermally treated, may preferably becombined with a further organometal metalloid compound, more preferablyan organoaluminum compound, most preferably a trialkylaluminum compoundin a suitable diluent or solvent, preferably one in which theorganometal compound is soluble. Typical solvents are hydrocarbonsolvents having from 5 to 12 carbon atoms, preferably aromatic solventssuch as toluene and xylenes, or aliphatic solvents of 6 to 10 carbonatoms, such as hexane, heptane, octane, nonane, decane, and isomersthereof, cycloaliphatic solvents of 6 to 12 carbon atoms such ascyclohexane, or mixtures of any of these.

The support material is combined with the organometal compound at atemperature of −20° C. to 150° C., preferably at 20° C. to 100° C. Thecontact time is not critical and can vary from 5 minutes to 72 hours,and is preferably from 0.5 hours to 36 hours. Agitation is preferablyapplied.

An alternative pretreatment of the support material involves a treatmentwith alumoxane. The alumoxane may be contacted with the support materialin the manner described above of the alumoxane may be generated in situon the support material by contacting an alkylaluminum, preferablytrialkylaluminum compound, with a support material containing water.

The pretreated support material is preferably recovered prior to itsfurther use.

Pretreated support material do not contain the tethering groups, suchas, for example, surface hydroxyl groups, which are typically found invarious support materials, especially silicas and silica containingsupport materials. Pretreated support materials may contain terminalresidues of a material used for pretreatment, such as, for example, analumoxane residue or the residue of a trialkylaluminum compound, such as—AlR2. Certain of these residues, in particular an alumoxane residue orthe residue of a trialkylaluminum compound, are capable of reacting withthe moiety having an active hydrogen of the anion (a)(2) of the ioniccompound. However, if a pretreated silica is used in a process, and atsome point in the process a compound which is the reaction product of(a) an ionic compound and (c) an organometal or metalloid compound, or asubstantially inactive catalyst precursor are brought into contact,reaction to form a covalent bond with tethering to the support is notpossible, since all potentially reactive groups which could enter into areaction resulting in tethering have been blocked or capped.

In various aspects of this invention where a support material isemployed, including catalyst components and catalysts, as well ascorresponding aspects which are nonsupported, whether as homogeneoussolutions, solids or dispersions, an alternative expression of each ofthose aspects is one that is essentially free of alumoxane.

According to the present invention, the ionic compound (a) can be formedinto a dispersion of solid particles (a) by a controlled precipitation.This dispersion can he used as such in the preparation of a solidcatalyst suitable for addition polymerization processes, therebymaintaining the dispersed nature. A range of suitable particle sizes forthe solid dispersed catalyst can be obtained by selecting the solventsand nonsolvents, temperature conditions and the specific catalystcomponents. No intermediate recovery or separation steps are requiredand the final solid catalyst, preferably still hi dispersed form, may beemployed as such in an addition polymerization process. Alternatively,the particulate solid (a) and the solid catalyst, and any solidintermediate product, can be recovered from the diluent in which it isdispersed by removing the liquid or nonsolvent employing techniques suchas filtration, vacuum drying, spray drying, and combinations thereof.Prior to its use, the particulate solid (a), the solid catalyst, and anysolid intermediate product, may be redispersed in a suitable liquiddiluent.

The catalyst component dispersion of the present invention can beprepared by converting a solution of the ionic compound (a), in adiluent (solvent) in which (a) is soluble, into a dispersion comprisingcomponent (a) in solid form.

It may be desirable to use a method wherein the converting is done inthe presence of (b) a transition metal compound and wherein the catalystcomponent is a substantially inactive catalyst precursor; or wherein theconverting, is clone in the presence of (c) an organometal or metalloidcompound wherein the metal or metalloid is selected from the Groups 1-14of the Periodic Table of the Elements and the catalyst component is areaction product of (a) and (c), or, alternatively, it may be desirableto employ the method such that the catalyst component excludes (b) atransition metal compound, excludes (c) an organometal or metalloidcompound wherein the metal or metalloid is selected from the Groups 1-14of the Periodic Table of the Elements, or excludes both (b) and (c).

A solution of ionic compound (a) in a diluent can be obtained by usingan appropriate solvent in which (a) is soluble. The diluent in which (a)is dissolved is not critical. Preferably, the diluent is compatible withthe other catalyst components and under polymerization conditions, sothat it does not need to be removed prior to its further use. Suitablesolvents for (a) include aromatic hydrocarbons, such as toluene,benzene, ethylbenzene, propylbenzene, butylbenzene, xylenes,chlorobenzene, and the like.

When a solvent is used in which (a) is not sufficiently soluble, or inorder to assist in or speed up dissolution of (a), heating may beapplied or solubilizing agents may be used, or a combination of both.The solubilizing agent to be used is compatible with the catalystcomponents, in a sense that it does not adversely affect the beneficialproperties of the catalyst. Heating is preferably done at temperaturesnot higher than the decomposition temperature of (a). During thedissolution of (a) stirring is advantageously applied.

Preferably, the solution of (a) contains from 0.0001 to 100 mole of (a)per liter, more preferably from 0.001 to 10 mole per liter. Anynondissolved (a) is preferably removed by, for example, filtrationtechniques, prior to further using the solution of (a).

The solution of (a) is then converted into a dispersion comprising (a)in solid form. The conversion of the solution of (a) to a dispersion of(a) can be carried out, for example, by a process wherein the dispersioncomprising component (a) is generated by cooling a solution of (a) in adiluent in which (a) is soluble, by contacting a solution of (a) in adiluent in which (a) is soluble with a diluent in which (a) is insolubleor sparingly soluble, by evaporating diluent from a solution of (a), byadding one or more precipitating agents to a solution of (a), or acombination of two or more of these techniques, to achieve a controlledprecipitation or solidification such that a dispersion of (a) is formed.It will be clear to a person skilled in the art that the distinctionbetween a solvent and a nonsolvent for a particular ionic compound (a)will primarily depend on the nature of the particular compound (a), onthe temperature, and relative amount of (a) to be dissolved. For a givenionic compound (a), the skilled person can easily determine what solventand temperature conditions are to be used to obtain a solution of thedesired concentration. On the other hand, given the solution of (a), theskilled person can easily determine the conditions and means to obtainthe dispersion of (a) having the desired solids concentration.

When precipitating agents are used, they are preferably compatible withthe catalyst components, such that the beneficial properties of thecatalyst are not adversely affected.

The nonsolvent employed for generating the dispersion of (a) is notcritical. Preferably, the nonsolvent is compatible with the othercatalyst components and under polymerization conditions, so that it doesnot need to be removed prior to further use. Preferred nonsolvents are,for example, pentane, hexane, heptane decane, dodecane, kerosene, andhigher aliphatic hydrocarbons of up to 30 carbon atoms.

The dispersion comprising component (a) is preferably generated bycontacting a solution of (a) in a diluent in which (a) is soluble with adiluent in which (a) is insoluble or sparingly soluble. The diluent inwhich (a) is soluble is preferably selected from the group consisting oftoluene, benzene, and xylenes, and the diluent in which (a) is insolubleor sparingly soluble is preferably selected from the group consisting ofpentane, hexane, heptane, and octane.

In contacting the solution of (a) with the nonsolvent, the amount ofnonsolvent is usually 10 to 10,000 parts by weight, preferably 100 to1,000 parts by weight per 100 parts by weight of the solution of (a).The contacting temperature is usually from −100 to 300° C., preferablyfrom −50 to 130° C., and most preferably from 10 to 110° C.

When the solvent, in which (a) is dissolved, needs to be removed aftercontacting with the nonsolvent, the solvent is preferably selected sothat it has a lower boiling point than that of the nonsolvent. Thesolvent can then be easily removed by heating the dispersion or byapplying reduced pressure.

The solid catalysts, either supported or nonsupported, according to thepresent invention can be prepared by combining, in any order, components(a), (b), (c), and optionally (d) in case of a supported catalyst,wherein during at least one step in the preparation of the solidcatalyst, component (a) dissolved in a diluent in which (a) is soluble,optionally in the presence of one or more of components (b), (c), and(d) or the contact product of (a) with one or more of (b), (c), and (d),is converted into solid form, optionally followed by recovering thesolid catalyst. After this step the other components (b), (c) andoptionally (d), to the extent they have not been added before, arecontacted with (a) in solid form, preferably dispersed in solid form.

According to an aspect of this invention, the methodology of which issimilar to that described above for the preparation of dispersions ofcatalyst components, it is desirable that during the at least one stepin the preparation of the solid catalyst, a dispersion comprisingcomponent (a) in solid form is generated by cooling a solution of (a) ina diluent in which (a) is soluble, by contacting a solution of (a) in adiluent in which (a) is soluble with a diluent in which (a) is insolubleor sparingly soluble, by evaporating diluent from a solution of (a), byadding one or mole precipitating agents to a solution of (a), or acombination of two or more of these techniques.

According to a preferred embodiment for the preparation of thenonsupported or supported solid catalyst, during the at least one stepin the preparation of the solid catalyst, a dispersion comprisingcomponent (a) in solid form is generated by contacting a solution of (a)in a diluent in which (a) is soluble, optionally in the presence of oneor more of components (b), (c), and (d) or the contact product of (a)with one or more of (b), (c), and (d), with a diluent in which (a) isinsoluble or sparingly soluble.

In all the process steps subsequent to the dispersion formation step, itis preferred not to use temperature conditions or types or quantities ofsolvents that would redissolve compound (a). The methods that can beused to generate the dispersion of (a) are essentially those which havebeen described above in relation to the formation of the catalystcomponent dispersion.

In the method for preparing the nonsupported or supported solidcatalyst, the dispersion comprising component (a) can be formed firstwhereupon the other components (b), (c), and optionally (d) can becombined in arbitrary order. Further, the dispersion comprisingcomponent (a) can be formed in the presence of one or more of the othercomponents (b), (c) and optionally (d). Exemplary embodiments are givenbelow.

In one embodiment for preparing the nonsupported or supported solidcatalyst,the dispersion comprising component (a) is first contacted withcomponent (b) and the resulting product is subsequently contacted withcomponent (c). Component (b) is preferably employed dissolved in asuitable solvent, such as a hydrocarbon solvent, advantageously a C₅₋₁₀aliphatic or cycloaliphatic hydrocarbon or a C₆₋₁₀ aromatic hydrocarbon.The contact temperature is not critical provided it is below thedecomposition temperature of the transition metal. Component (c) can beused in a neat form, that is, as is, or dissolved in a hydrocarbonsolvent, which may be similar to the one used for dissolving component(b).

In a further embodiment for preparing the nonsupported or supportedsolid catalyst, components (b) and (c) are first contacted, preferablyin a suitable solvent, and then contacting the resulting product withthe dispersion comprising component (a). The solvent or solvents usedfor contacting (b) and (c) are of such nature or are used in suchquantities, or a combination thereof, that when the resulting product iscontacted with the dispersion comprising (a), component (a) is notsubstantially redissolved.

In some of the methods of preparing a supported solid catalyst,including the precipitation methods described above, the manner in whichcomponent (d) is added is not critical. Component (d) can he addedduring one of the steps in the preparation of the solid catalyst. Thesupport material (d) can be added after the components (a), (b), and (c)have been combined with each other, or (d) can be combined with at leastone of the components prior to combining the resulting product with theremaining component or components.

According to a preferred embodiment for the preparation of a supportedsolid catalyst, component (a) dissolved in a solvent is first combinedwith component (d), whereupon a dispersion of (a) is generated in themanner as described above in relation to the generation of thedispersion of (a). The combining of component (d) with the solution ofcomponent (a) may be carried out while forming a slurry, that is, usingan excess amount of liquid, or alternatively, only so much of thesolution of component (a) is used that no slurry is formed.Advantageously in the latter situation, the volume of the solution ofcomponent (a) does not exceed substantially, and is preferably aboutequal to, the pore volume of component (d). After this contacting step,component (a) is converted into solid form, preferably by combining thecontact product of (a) and (d) with a diluent in which (a) is insolubleor sparingly soluble. The amount of solids relative to the amount ofnonsolvent is not critical but typically is from 0.001 to 50 weightpercent.

When component (d) is contacted with a solution of (a), (d) ispreferably used after it has been pretreated to remove substantially allwater and surface hydroxyl groups, and especially by treatment with analuminumalkyl, more preferably with an aluminumtrialkyl compound. It isadvantageous to contact the solution of (a) with component (c),preferably with one molar equivalent of (c), prior to contacting thesame with component (d). A highly preferred support material for use inthese embodiments is pretreated silica.

Typical, yet not critical, temperatures for any of the steps except thedispersion formation step are −50 to 150° C. Preferably, each of thecontacting steps is carried out while stirring or agitating. All stepsin the present process should be conducted in the absence of oxygen andmoisture.

In an alternative method for the preparation of solid supportedcatalysts, it is desirable that the support material used is apretreated support material with a pore volume of from 0.1 to 5 cm³/gand in the supported catalyst the anion (a)(2) is not chemically bondedto the support (d), and wherein the volume of the solution of (a),optionally in the presence of one or both of (b) and (c), is from 20volume percent to 200 volume percent of the total pore volume of thesupport material used. Preferred embodiments are those wherein thevolume of the solution is from 70 (volume percent to 130 volume percentof the total pore volume of the support material used, or wherein thevolume of the solution is substantially equal to the total pore volumeof the support material used. Some aspects of this method may be similarto various aspects of processes for the preparation of supportedcatalyst, variously referred to as incipient impregnation or incipientwetness techniques, as disclosed in U.S. Pat. Nos. 5.602,067; 5,625,015;and PCT applications WO-95/12622; WO-96/23005; WO-96/16093; WO-97/02297;and WO-97/24375, all of which are hereby incorporated by reference.

In alternative aspects of this embodiment, as mentioned in the twoparagraphs immediately above, it may be desirable that the solution of(a) is produced in the presence of (b), or in the presence of (c), or inthe presence of (b) and (c).

Generally, in this aspect it is desirable that the solid catalyst isproduced by adding the solution of (a), optionally containing one orboth of (b) and (c), to substantially dry pretreated support material,followed by removal of the diluent.

In another alternative for the preparation of the supported catalyst, itis desirable that the support material used is a pretreated supportmaterial with a pore volume of from 0.1 to 5 cm³/g and in the supportedcatalyst the anion (a)(2) is not chemically bonded to the support (d),and wherein the volume of the solution of (a), optionally in thepresence of one or both of (b) and (c), is greater than 200 volumepercent of the total pore volume of the support material used. Inalternative aspects of this embodiment, it may be desirable that thesolution of (a) is produced in the presence of (b), or in the presenceof (c), or in the presence of (b) and (c). In this aspect it may bedesirable that the solid catalyst is produced by adding the solution of(a), optionally containing one or both (b) and (c), to substantially drypretreated support material, followed by removal of the diluent, or itmay be added to a slurry of (d) in a diluent, followed by removal of thediluent.

The nonsupported or supported solid catalyst may be stored or shipped infree flowing form under inert conditions after removal of the solvent.

The combining of components (a) and (b) in equimolar amounts does notresult in a catalyst composition that has substantial activity inaddition polymerization processes. Upon combining this composition withcomponent (c) an active catalyst composition is surprisingly formed.Therefore, a further embodiment provides a method for activating asubstantially inactive catalyst precursor to form a catalyst suitablefor addition polymerization wherein a substantially inactive catalystprecursor comprising an ionic compound (a) and a transition metalcompound (b) and, optionally, component (d), is contacted withorganometal compound (c) to form an active catalyst. In one aspect,preferably, the substantially inactive catalyst precursor is in a solidform, either supported or nonsupported, more preferably dispersed in adiluent, while in an alternative aspect wherein no support is used allthe materials are used in solution form and the activation processproduced a homogenous solution of a catalyst suitable for solutionpolymerization.

Preferably, according to this activating method, a dispersion of anonsupported or supported solid substantially inactive catalystprecursor, comprising (a),(b) and optionally (d), and the organometalcompound (c) are each separately added, preferably directly, into anaddition polymerization reactor containing addition polymerizablemonomer or monomers, preferably under addition polymerizable conditions.The catalyst components can be added separately to the reactor or tospecific locations in the reactor which enables the catalyst to beactivated only in the reactor or in a specific location in the reactor,which offers a more controllable polymerization reaction. This isespecially advantageous where the addition polymerization reactor isoperated under slurry phase or gas phase polymerization conditions.

The relative amounts of the components to be used in the compositionsand processes of the present invention will now be described. Therelative amount of ionic compound (a) to gramatoms of transition metalin compound (b), is not critical but generally is in the range from 0.1to 500 mole of (a) per gramatoms of (b). Preferably, 0.5 to 100 mole of(a) per gramatoms of (b) is used, most preferably from about 1 to 3 moleof (a) per gramatoms of (b).

The ratio between organometal compound (c) and the ionic compound (a) isnot critical, but generally lies within the range of 0.05 to 1,000 moleof (c) per mole of (a). Preferably, the ratio is from 0.5 to 100 mole(c) per mole (a), most preferably from about 1 to 50 mole (c) per mole(a).

The amount of optional component (d) to be used in the present inventionis also not critical, however, typical values range from 0.1 μmol to 2mmol of ionic compound (a) per gram of support material. Preferably,from 10 to 1,000 μmol of ionic compound (a) is used per gram of supportmaterial.

The solid catalyst can be used as such or after being subjected toprepolymerization. The prepolymerization can be carried out by any knownmethods such as by bringing a small amount of one or more polymerizablemonomers into contact with the solid catalyst. The monomers which can beused in the prepolymerization are not particularly limited and includethe olefins and diolefins mentioned hereinafter. It is preferable to usefor the prepolymerization the same monomer as used in the subsequentpolymerization. The prepolymerization temperature may usually range from−20° C. to 100° C., preferably from −10 to 70° C. more preferably from 0to 50° C.

The prepolymerization may be carried out batchwise or continuously underatmospheric pressure or elevated pressures. The prepolymerization may becarried out in the presence of a molecular weight controlling agent suchas hydrogen. The prepolymerization is carried out in the absence orpresence of a solvent or diluent. When a solvent or diluent is used itis preferably an inert hydrocarbon, such as the ones describedhereinafter with respect to the polymerization process. Preferably thesolvent or diluent used does not substantially redissolve the solidcatalyst comprising ionic compound (a). The prepolymerization istypically carried out to form a prepolymerized catalyst, that is polymeris formed on the solid catalyst particles, having from 0.1 to 100 g ofpolymer per 1 g of solid catalyst, preferably from 1 to 10 g of polymerper g of solid catalyst. Typical particle sizes of prepolymerizedcatalysts are in the range of 1 to 200 μm, preferably in the range from10 to 100 μm.

The solid catalysts of the present invention, optionally prepolymerized,may be used in an addition polymerization process wherein one or moreaddition polymerizable monomers are contacted with the solid catalyst ofthe invention under addition polymerization conditions.

Suitable addition polymerizable monomers include ethylenicallyunsaturated monomers, acetylenic compounds, conjugated or nonconjugateddienes, polyenes, and carbon monoxide. Preferred monomers includeolefins, for examples alpha-olefins having from 2 to about 20,preferably from about 2 to about 12, more preferably from about 2 toabout 8 carbon atoms and combinations of two or more of suchalpha-olefins. Particularly suitable alpha-olefins include, for example,ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof.Preferably, the alpha-olefins are ethylene, propylene, 1-butene,4-methyl-pentene-1, 1-pentene, 1-hexene, 1-octene, and combinations ofethylene and/or propylene with one or more of such other alpha-olefins.Most preferably, ethylene or propylene is used as one of the additionpolymerizable monomers. Suitable dienes include those having from 4 to30 carbon atoms, especially those having 5 to 18 carbon atoms. Typicalof these are α,ω-dienes, α-internal dienes, including those dienes whichare typically used for preparing EPDM type elastomers. Typical examplesinclude 1,3-butadiene, 1,3- and 1,4-pentadiene, 1,3-, 1,4-, and1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, and lower alkyl substitutedanalogues of any of these. Other preferred monomers include styrene,halo- or alkyl substituted styrenes, tetrafluoroethylene,vinylcyclobutene, dicyclopentadiene, and ethylidene norbornenes.Suitable addition polymerizable monomers include also any mixtures ofthe above-mentioned monomers.

The solid catalyst can be formed in situ in the polymerization mixtureby introducing into the mixture the catalyst components (a), (b), (c),and optionally (d).

The solid catalysts of this invention, both supported and nonsupported,as well as the homogeneous catalysts, may he used in various catalystssystems, either alone or with other catalyst components or othercatalysts, where the catalyst of this invention is an integral part ofthe catalyst system.

The catalyst may be used in the polymerization reaction in aconcentration of 10⁻⁹ to 10⁻³ moles, based on transition metal, perliter diluent or reaction volume, but is preferably used in aconcentration of less than 10⁻⁵, preferably from 10⁻⁸ to 9×10⁻⁶ molesper liter diluent or reaction volume.

The solid catalysts can be advantageously employed in a high pressure,solution, slurry, or gas phase polymerization process. For a solutionpolymerization process it is desirable to redissolve the solid catalystor to employ homogeneous solutions of the catalyst components. A highpressure process is usually carried out at temperatures from 100° C. to400° C. and at pressures above 500 bar. A slurry process typically usesan inert hydrocarbon diluent and temperatures of from about 0° C. up toa temperature just below the temperature at which the resulting polymerbecomes substantially soluble in the inert polymerization medium.Preferred temperatures are from about 30° C., preferably from about 60°C. to about 115° C., preferably to about 100° C. The solution process iscarried out at temperatures from the temperature at which the resultingpolymer is soluble in an inert solvent up to about 275° C. Generally,solubility of the polymer depends on its density. For ethylenecopolymers having densities of 0.86 g/cm³, solution polymerization maybe achieved at temperatures as low as about 60° C. Preferably, solutionpolymerization temperatures range from about 75° C., more preferablyfrom about 80° C., and typically from about 130° C. to about 260° C.,more preferably to about 170° C. Most preferably, temperatures in asolution process are between about 80° C. and 150° C. As inert solventstypically hydrocarbons and preferably aliphatic hydrocarbons are used.The solution and slurry processes are usually carried out at pressuresbetween about 1 to 100 bar. Typical operating conditions for gas phasepolymerizations are from 20° C. to 100° C., more preferably from 40° C.to 80° C. In gas phase processes the pressure is typically fromsubatmospheric to 100 bar.

Preferably for use in gas phase polymerization processes, the solidcatalyst has a median particle diameter from about 20 to about 200 μm,more preferably from about 30 μm to about 150 μm, and most preferablyfrom about 50 μm to about 100 μm. Preferably for use in slurrypolymerization processes, the support has a median particle diameterfrom about 1 μm to about 200 μm, more preferably from about 5 μm toabout 100 μm, and most preferably from about 10 μm to about 80 μm.Preferably for use in solution or high pressure polymerizationprocesses, the support has a median particle diameter from about 1 μm toabout 40 μm, more preferably from about 2 μm to about 30 μm, and mostpreferably from about 3 μm to about 20 μm.

In the polymerization processes of the present invention impurityscavengers may be used which serve to protect the solid catalyst fromcatalyst poisons such as water, oxygen, and polar compounds. Thesescavengers can generally be used in amounts depending on the amounts ofimpurities. Typical scavengers include organometal compounds, andpreferably trialkylaluminum or boron compounds and alumoxanes. Further,antistatic agents may be introduced into the reactor to preventagglomeration or sticking of polymer or catalyst to the reactor walls.

In the present polymerization processes also molecular weight controlagents can be used, such as hydrogen or other chain transfer agents. Thepolymers that are prepared according to such polymerization process maybe combined with any conventional additives, such as UV stabilizers,antioxidants, anti-slip or anti-blocking agents, which may be added inconventional ways, for example, downstream of the polymerizationreactor, or in an extrusion or molding step.

Upon or after removal of the polymerization mixture or product of fromthe polymerization reactor, the supported catalyst may be deactivated byexposure to air or water, or through ally other catalyst deactivatingagent or procedure.

Suitable solvents for the various polymerization processes are inertliquids. Examples include straight and branched-chain hydrocarbons suchas isobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and the like and aromatic and alkyl-substituted aromaticcompounds such as benzene, toluene, xylene, ethylbenzene and the like.Suitable solvents also include liquid olefins which may act as monomersor comonomers including ethylene, propylene, butadiene, 1-butene,cyclopentene, 1-hexene, 1-heptene, 4-vinylcyclohexene, vinylcyclohexane,3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene,1-decene, styrenes divinylbenzene, allylbenzene, vinyltoluene (includingall isomers alone or in admixture), and the like. Mixtures of theforegoing are also suitable.

The catalyst systems may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst inseparate reactors connected in series or in parallel to prepare polymerblends having desirable properties. An example of such a process isdisclosed in WO-94/00500, equivalent to U.S. Ser. No. 07/904.770, aswell as U.S. Ser. No. 08/10958, filed Jan. 29, 1993, the teachings ofwhich are hereby incorporated by reference herein.

Utilizing, the catalyst systems of the present invention, particularlyfor solution polymerization, copolymers having high comonomerincorporation and correspondingly low density, yet having a low meltindex may be readily prepared. That is, high molecular weight polymersare readily attained by use of the present catalysts even at elevatedreactor temperatures. This result is highly desirable because themolecular weight of α-olefin copolymers can be readily reduced by theuse of hydrogen or similar chain transfer agent, however increasing themolecular weight of α-olefin copolymers is usually only attainable byreducing the polymerization temperature of the reactor.Disadvantageously, operation of a polymerization reactor at reducedtemperatures significantly increases the cost of operation since heatmust be removed from the reactor to maintain the reduced reactiontemperature, while at the same time heat must be added to the reactoreffluent to vaporize the solvent. In addition, productivity is increaseddue to improved polymer solubility, decreased solution viscosity, and ahigher polymer concentration. Utilizing the present catalysts, α-olefinin homopolymers and copolymers having densities from 0.85 g/cm³ to 0.96g/cm³, and melt flow rates from 0.001 to 10.0 dg/min are readilyattained in a high temperature process.

The solid catalysts of the present invention, also when used in a slurryprocess or gas phase process, not only are able to produce ethylenecopolymers of densities typical for high density polyethylene, in therange of 0.980 to 0.940 g/cm³, but surprisingly, also enable theproduction of copolymers having substantially lower densities.Copolymers of densities lower than 0.940 g/cm³ and especially lower than0.930 g/cm³ down to 0.880 g/cm³ or lower can be made while providingfree flowing polymers, retaining good bulk density properties and whilepreventing or substantially eliminating reactor fouling. The presentinvention is capable of producing olefin polymers and copolymers havingweight average molecular weights of more than 30,000, preferably morethan 50,000, most preferably more than 100,000 up to 1,000,000 and evenhigher. Typical molecular weight distributions M_(w)/M_(n) range from1.5 to 15, or even higher, preferably between 2.0 and 8.0.

The catalyst systems of the present invention are particularlyadvantageous for the production of ethylene homopolymers andethylene/α-olefin copolymers having high levels of long chain branching,especially in solution polymerizations and in gas phase polymerizationprocesses. The use of the catalyst systems of the present invention incontinuous polymerization processes, especially continuous, solutionpolymerization processes, allows for elevated reactor temperatures whichfavor the formation of vinyl terminated polymer chains that may beincorporated into a growing polymer, thereby giving a long chain branch.The use of the present catalysts system advantageously allows for theeconomical production of ethylene/α-olefin copolymers havingprocessability similar to high pressure, free radical produced lowdensity polyethylene.

In another aspect of the processes of this invention, a preferredprocess is a high temperature solution polymerization process for thepolymerization of olefins comprising contacting one or more C₂₋₂₀α-olefins under polymerization conditions 25 with a catalyst system ofthis invention at a temperature from about 100° C. to about 250° C. Morepreferred as a temperature range for this process is a temperature fromabout 120° C. to about 200° C., and even more preferred is temperaturefrom about 150° C. to about 200° C.

The present catalysts system may be advantageously employed to prepareolefin polymers having improved processing properties by polymerizingethylene alone or ethylene/α-olefin mixtures with low levels of a “H”branch inducing diene, such as norbornadiene, 1,7-octadiene, or1,9-decadiene. The unique combination of elevated reactor temperatures,high molecular weight (or low melt indices) at high reactor temperaturesand high comonomer reactivity advantageously allows for the economicalproduction of polymers having excellent physical properties andprocessability. Preferably such polymers comprise a C₃₋₂₀ α-olefin,including ethylene, and a “H”-branching comonomer. Preferably, suchpolymers are produced in a solution process, most preferably acontinuous solution process. Alternatively, such polymers may beproduced in a gas phase process or a slurry process, as disclosed inU.S. application Ser. No. 08/857817 filed May 16, 1997; U.S. applicationSer. No. 08/857816 filed May 16, 1997; and PCT Application No.PCT/US97/08466 filed May 16, 1997, all of which are hereby incorporatedby reference.

As previously mentioned, the present catalyst system is particularlyuseful in the preparation of EP and EPDM copolymers in high yield andproductivity. The process employed may be either a solution or slurryprocess both of which are previously known in the art. Kaminsky, J.Poly. Sci., Vol. 23, pp. 2151-64 (1985) reported the use of a solublebis(cyclopentadienyl) zirconium dimethyl-alumoxane catalyst system forsolution polymerization of EP and EPDM elastomers. U.S. Pat. No.5,229,478 disclosed a slurry polymerization process utilizing similarbis(cyclopentadienyl) zirconium based catalyst systems.

In general terms, it is desirable to produce such EP and EPDM elastomersunder conditions of increased reactivity of the diene monomer component.The reason for this was explained in the above-identified '478 patent inthe following manner, which still remains true despite the advancesattained in such reference. A major factor affecting production costsand hence the utility of an EPDM is the diene monomer cost. The diene isa more expensive monomer material than ethylene or propylene. Further,the reactivity of diene monomers with previously known metallocenecatalysts is lower than that of ethylene and propylene. Consequently, toachieve the requisite degree of diene incorporation to produce an EPDMwith an acceptably fast cure rate, it has been necessary to use a dienemonomer concentration which, expressed as a percentage of the totalconcentration of monomers present, is in substantial excess compared tothe percentage of diene desired to be incorporated into the final EPDMproduct. Since substantial amounts of unreacted diene monomer must berecovered from the polymerization reactor effluent for recycle, the costof production is increased unnecessarily.

Further adding to the cost of producing an EPDM is the fact that,generally, the exposure of an olelin polymerization catalyst to a diene,especially the high concentrations of diene monomer required to producethe requisite level of diene incorporation in the final EPDM product,often reduces the rate or activity at which the catalyst will causepolymerization of ethylene and propylene monomers to proceed.Correspondingly, lower throughputs and longer reaction times have beenrequired. compared to the production of an ethylene-propylene copolymerelastomer or other α-olefin copolymer elastomer.

The present catalyst system advantageously allows for increased dienereactivity thereby preparing EPDM polymers in high yield andproductivity. Additionally, the catalyst system of the present inventionachieves the economical production of EPDM polymers with diene contentsof up to 20 weight percent or higher, which polymers possess highlydesirable fast cure rates.

The nonconjugated diene monomer can be a straight chain, branched chainor cyclic hydrocarbon diene having from about 6 to about 15 carbonatoms. Examples of suitable nonconjugated dienes are straight chainacyclic dienes such as 1,4-hexadiene and 1,6-octadiene: branched chainacyclic dienes such as 5-methyl-1,4-hexadiene;3,7-dimethyl-1,6-octadiene: 3,7-dimethyl-1,7-octadiene and mixed isomersof dihydromyricene and dihydroocinene; single ring alicyclic dienes suchas 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene: and multi-ring alicyclic fused and bridged ringdienes such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene; bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene. 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.

Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

The preferred EPDM elastomers may contain about 20 up to about 90 weightpercent ethylene, more preferably about 30 to 85 weight percentethylene, most preferably about 35 to about 80 weight percent ethylene.

The alpha-olefins suitable for use in the preparation of elastomers withethylene and dienes are preferably C₃₋₁₆ alpha-olefins. Illustrativenonlimiting examples of such alpha-olefins are propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,and 1-dodecene. The alpha-olefin is generally incorporated into the EPDMpolymer at about 10 to about 80 weight percent, more preferably at about20 to about 65 weight percent. The nonconjugated dienes are generallyincorporated into the EPDM at about 0.5 to about 20 weight percent;more, preferably at about 1 to about 15 weight percent, and mostpreferably at 3 to about 12 weight percent. If desired, more than onediene may be incorporated simultaneously, for example HD and ENB, withtotal diene incorporation within the limits specified above.

At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture-free atmosphere. Preferably,therefore, the reactions are performed in the presence of a dry, inertgas such as, for example. nitrogen.

The polymerization may be carried out as a batchwise or a continuouspolymerization process. A continuous process is preferred, in whichevent catalyst components, ethylene, α-olefin, and optionally solventand diene are continuously supplied to the reaction zone and polymerproduct continuously removed therefrom. Within the scope of the terms“continuous” and “continuously” as used in this context are thoseprocesses in which there are intermittent additions of reactants andremoval of products at small regular intervals, so that, over time theoverall process is continuous.

In a preferred manner of operation, the polymerization is conducted in acontinuous solution polymerization system comprising two reactorsconnected in series or parallel. In one reactor a relatively highmolecular weight product (Mw from 300,000 to 600,000, more preferably400,000 to 500,000) is formed while in the second reactor a product of arelatively low molecular weight (Mw 50,000 to 300,000) is formed. Thefinal product is a blend of the two reactor effluents which are combinedprior to devolatilization to result in a uniform blend of the twopolymer products. Such a dual reactor process allows for the preparationof products having, improved properties. In a preferred embodiment thereactors are connected in series, that is effluent from the firstreactor is charged to the second reactor and fresh monomer, solvent andhydrogen is added to the second reactor. Reactor conditions are adjustedsuch that the weight ratio of polymer produced in the first reactor tothat produced in the second reactor is from 20:80 to 80:20. In additionthe temperature of the second reactor is controlled to produce the lowermolecular weight product. This system beneficially allow for productionof EPDM products having a large range of Mooney viscosities, as well asexcellent strength and processability. Preferably the Mooney viscosity(ASTM D1646-94, ML1+4@125° C.) of the resulting product is adjusted tofail in the range from 1 to 200, preferably from 5 to 150 and mostpreferably from 10 to 110.

The polymerization process of the present invention can he employed toadvantage in the gas phase copolymerization of olefins. Gas phaseprocesses for the polymerization of olefins, especially thehomopolymerization and copolymerization of ethylene and propylene, andthe copolymerization of ethylene with higher α-olefins such as, forexample, 1-butene, 1-hexene, 4-methyl-1-pentene are well known in theart. Such processes are used commercially on a large scale for themanufacture of high density polyethylene (HIDPE), medium densitypolyethylene (MDPE), linear low density polyethylene (LLDPE) andpolypropylene.

The gas phase process employed can be, for example, of the type whichemploys a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported or suspended above a perforated plate, the fluidization grid,by a flow of fluidization gas.

The gas employed to fluidize the bed comprises the monomer or monomersto be polymerized, and also serves as a heat exchange medium to removethe heat of reaction from the bed. The hot gases emerge from the top ofthe reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means or a blower orcompressor and one or more heat exchangers to strip the gas of the heatof polymerization.

A preferred method of cooling of the bed, in addition to the coolingprovided by the cooled recycle gas, is to feed a volatile liquid to thebed to provide an evaporative cooling effect, often referred to asoperation in the condensing mode. The volatile liquid employed in thiscase can be, for example, a volatile inert liquid, for example, asaturated hydrocarbon having about 3 to about 8, preferably 4 to 6,carbon atoms. In the case that the monomer or comonomer itself is avolatile liquid, or can be condensed to provide such a liquid this cansuitably be fed to the bed to provide an evaporative cooling effect.Examples of olefin monomers which can be employed in this manner areolefins containing about three to about eight, preferably three to sixcarbon atoms. The volatile liquid evaporates in the hot fluidized bed toform gas which mixes with the fluidizing gas. If the volatile liquid isa monomer or comonomer, it will undergo some polymerization in the bed.The evaporated liquid then emerges from the reactor as part of the hotrecycle as, and enters the compression/heat exchange part of the recycleloop. The recycle gas is cooled in the heat exchanger and, if thetemperature to which the gas is cooled is below the dew point, liquidwill precipitate from the gas. This liquid is desirably recycledcontinuously to the fluidized bed. It is possible to recycle theprecipitated liquid to the bed as liquid droplets carried in the recyclegas stream. This type of process is described, for example in EP-8969 1;U.S. Pat. No. 4,543,399; WO-94/25495 and U.S. Pat. No. 5,352,749, whichare hereby incorporated by reference. A particularly preferred method ofrecycling the liquid to the bed is to separate the liquid from therecycle gas stream and to reinject this liquid directly into the bed,preferably using a method which generates fine droplets of the liquidwithin the bed. This type of process is described in BP Chemicals'WO-94/28032, which is hereby incorporated by reference.

The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalyst.Such catalyst can be supported on an inorganic or organic supportmaterial as described above. The catalyst can also be subjected to aprepolymerization step, for example, by polymerizing a small quantity ofolefin monomer in a liquid inert diluent, to provide a catalystcomposite comprising catalyst particles embedded in olefin polymerparticles.

The polymer is produced directly in the fluidized bed by catalyzedcopolymerization of the monomer and one or more comonomers on thefluidized particles of catalyst, supported catalyst or prepolymer withinthe bed. Start-up of the polymerization reaction is achieved using a bedof preformed polymer particles, which are preferably similar to thetarget polyolefin, and conditioning the bed by drying with inert gas ornitrogen prior to introducing the catalyst, the monomers and any othergases which it is desired to have in the recycle gas stream, such as adiluent gas, hydrogen chain transfer agent, or an inert condensable gaswhen operating in gas phase condensing mode. The produced polymer isdischarged continuously or discontinuously from the fluidized bed asdesired.

The gas phase processes suitable for the practice of this invention arepreferably continuous processes which provide for the continuous supplyof reactants to the reaction zone of the reactor and the removal ofproducts from the reaction zone of the reactor, thereby providing asteady-state environment on the macro scale in the reaction zone of thereactor.

Typically, the fluidized bed of the gas phase process is operated attemperatures greater than 50° C., preferably from about 60° C. to about110° C., more preferably from about 70° C. to about 110° C.

Typically the molar ratio of comonomer to monomers used in thepolymerization depends upon the desired density for the compositionbeing produced and is about 0.5 or less. Desirably, when producingmaterials with a density range of from about 0.91 to about 0.93 thecomonomer to monomer ratio is less than 0.2, preferably less than 0.05,even more preferably less than 0.02, and may even be less than 0.01.Typically, the ratio of hydrogen to monomer is less than about 0.5,preferably less than 0.2, mote preferably less than 0.05, even morepreferably less than 0.02 and may even he less than 0.01.

The above-described ranges of process variables are appropriate for thegas phase process of this invention and may be suitable for otherprocesses adaptable to the practice of this invention.

A number of patents and patent applications describe gas phase processeswhich are adaptable for use in the process of this invention,particularly, U.S. Pat. Nos. 4,588,790; 4,543,399; 5,352,749; 5,436,304;5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670;5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; 5,616,661; and EPapplications 659,773; 692,500; 780,404; 697,420; 628,343; 593,083;676,421; 683,176; 699,212; 699,213; 721,798; 728;150: 728,151; 728,771;728,772; 735,058; and PCT Applications WO-94/29032, WO-94/25497,WO-94/25495, WO-94/28032, WO-95/13305, WO-94/26793, WO-95/07942,WO-97/25355, WO-93/11171, WO-95/13305, and WO-95/13306, all of which arehereby incorporated herein by reference.

For the preferred polyolefin polymer compositions of this invention,which may be produced by the polymerization processes of this inventionusing the catalyst systems of this invention, the long chain branch islonger than the short chain branch that results from the incorporationof one or more α-olefin comonomers into the polymer backbone. Theempirical effect of the presence of long chain branching in thecopolymers of this invention is manifested as enhanced rheologicalproperties which are indicated by higher flow activation energies, andgreater I₂₁/I₂ than expected from the other structural properties of thecompositions.

Further, highly preferred polyolefin copolymer compositions of thisinvention have reverse molecular architecture, that is, there is amolecular weight maximum which occurs in that 50 percent by weight ofthe composition which has the highest weight percent comonomer content.Even more preferred are polyolefin copolymer compositions which alsohalve long chain branches along the polymer backbone, especially whenproduced with a catalyst system of this invention having a singlemetallocene complex of this invention in a single reactor in a processfor the polymerization of all α-olefin monomer with one or more olefincomonomers, more especially when the process is a continuous process.

Measurement of Comonomer Content vs. Log Molecular Weight by GPC/FTIR

The comonomer content as a function of molecular weight was measured bycoupling a Fourier transform infrared spectrometer (FTIR) to a Waters150° C. Gel Permeation Chromatograph (GPC). The setting up, calibrationand operation of this system together with the method for data treatmenthas been described previously (L. J. Rose et al, “Characterisation ofPolyethylene Copolymers by Coupled GPC/FTIR” in “Characterisation ofCopolymers”, Rapra Technology, Shawbury UK, 1995, ISBN 1-85957-048-86.)In order to characterize the degree to which the comonomer isconcentrated in the high molecular weight part of the polymer, theGPC/FTIR was used to calculate a parameter named comonomer partitionfactor, C_(pf). M_(n) and M_(w) were also determined using standardtechniques from the GPC data.

Comonomer Partitioning Factor (GPC-FTIR)

The comonomer partitioning factor C_(pf) is calculated from GPC/FTIRdata. It characterizes the ratio of the average comonomer content of thehigher molecular weight fractions to the average comonomer content ofthe lower molecular weight fractions. Higher and lower molecular weightare defined as being above or below the median molecular weightrespectively, that is, the molecular weight distribution is divided intotwo parts of equal weight. C_(pf) is calculated from the followingequation:${C_{pf} = \frac{\frac{\sum\limits_{i = 1}^{n}{w_{i} \cdot c_{i}}}{\sum\limits_{i = 1}^{n}w_{i}}}{\frac{\sum\limits_{j = 1}^{m}{w_{j} \cdot c_{j}}}{\sum\limits_{j = 1}^{m}w_{j}}}},$

where: c_(i) is the mole fraction comonomer content and w_(i) is thenormalized weight fraction as determined by GPC/FTIR for the n FTIR datapoints above the median molecular weight, c_(j) is the mole fractioncomonomer content and w_(j) is the normalized weight fraction asdetermined by GPC/FTIR for the m FTIR data points below the medianmolecular weight. Only those weight fractions, w_(i) or w_(j) which haveassociated mole fraction comonomer, content values are used to calculateC_(pf). For a valid calculation it is required that n and m are greaterthan or equal to 3. FTIR data corresponding to molecular weightfractions below 5,000 are not included in the calculation due to theuncertainties present in such data.

For the polyolefin copolymer compositions of this invention, C_(pf)desirably is equal to or greater than 1.10, more desirably is equal toor greater than 1.15, even more desirably is equal to or greater than1.20, preferably is equal to or greater than 1.30, more preferably isequal to or greater than 1.40, even more preferably is equal to orgreater than 1.50, and still more preferably is equal to or greater than1.60.

ATREF-DV

ATREF-DV has been described in U.S. Pat. No. 4,79,081, which is herebyincorporated by reference, and in “Determination of Short-ChainBranching Distributions of Ethylene copolymers by Automated AnalyticalTemperature Rising Elution Fractionation” (Auto-ATREF), J. of Appl PolSci: Applied Polymer Symposium 45, 25-37 (1990). ATREF-DV is a dualdetector analytical system that is capable of fractionatingsemi-crystalline polymers like Linear Low Density Polyethylene (LLDPE)as a function of crystallization temperature while simultaneouslyestimating the molecular weight of the fractions. With regard to thefractionation, ATREF-DV is analogous to Temperature Rising ElutionFractionation (TREF) analysis that have been published in the openliterature over the past 15 years. The primary difference is that thisAnalytical—TREF (ATREF) technique is done on a small scale and fractionsare not actually isolated. Instead, a typical liquid chromatographic(LC) mass detector, such as an infrared single frequency detector isused to quantify the crystallinity distribution as a function of elutiontemperature. This distribution can then be transformed to any number ofalternative domains such as short branching frequency, comonomerdistribution, or possibly density. Thus, this transformed distributioncan then be interpreted according to some structural variable likecomonomer content, although routine use of ATREF for comparisons ofvarious LLDPE's is often done directly in the elution temperaturedomain.

To obtain ATREF-DV data, a commercially available viscometer especiallyadapted for LC analysis, such as a Viskotek™ is coupled with the IR massdetector. Together these two LC detectors can be used to calculate theintrinsic viscosity of the ATREF-DV eluant. The viscosity averagemolecular weight of a given fraction can then be estimated usingappropriate Mark Hoodwink constants, the corresponding intrinsicviscosity, and suitable coefficients to estimate the fractionsconcentration (dl/g) as it passes through the detectors. Thus, a typicalATREF-DV report will provide the weight fraction polymer and viscosityaverage molecular weight as a function of elution temperature. M_(pf) isthen calculated using the equation given.

Molecular Weight Partitioning Factor

The molecular weight partitioning factor M_(pf) is calculated fromTREF/DV data. It characterizes the ratio of the average molecular weightof the fractions with high comonomer content to the average molecularweight of the fractions with low comonomer content. Higher and lowercomonomer content are defined as being below or above the median elutiontemperature of the TREF concentration plot respectively, that is, theTREF data is divided into two parts of equal weight. M_(pf) iscalculated from the following equation:${M_{pf} = \frac{\frac{\sum\limits_{i = 1}^{n}{w_{i} \cdot M_{i}}}{\sum\limits_{i = 1}^{n}w_{i}}}{\frac{\sum\limits_{j = 1}^{m}{w_{j} \cdot M_{j}}}{\sum\limits_{j = 1}^{m}w_{j}}}},$

where: M_(i) is the viscosity average molecular weight and w_(i) is thenormalized weight fraction as determined by ATREF-DV for the n datapoints in the fractions below the median elution temperature. M_(j) isthe viscosity average molecular weight and w_(j) is the normalizedweight fraction as determined by ATREF- DV for the m data points in thefractions above the median elution temperature. Only those weightfractions, w_(i) or w_(j) which have associated viscosity averagemolecular weights greater than zero are used to calculate M_(pf). For avalid calculation, it is required that n and m ale greater than or equalto 3.

For the polyolefin copolymer compositions of this invention, M_(pf)desirably is equal to or greater than 1.15, more desirably is equal toor greater than 1.30, even more desirably is equal to or greater than1.40, preferably is equal to or greater than 1.50, more preferably isequal to or greater than 1.60, even more preferably is equal to orgreater than 1.70.

Having described the invention the following examples are provided asfurther illustration thereof and are not to be construed as limiting.Unless stated to the contrary all parts and percentages are expressed ona weight basis.

EXAMPLES

The bulk density of the polymers produced in the present examples wasdetermined according to ASTM 1895. All experiments were carried outunder the exclusion of oxygen and water under a nitrogen atmosphere,unless indicated otherwise.

Preparation of the Hydrochloride of Kemnamine™ T9701

Kemamine™ T9701, (NMe(C₁₈₋₂₂H₃₇₋₄₅)₂(13.4 gram, 25 mmol), available fromWitco Corp. (Kemamine is a trademark of Witco Corp.) was dissolved indiethylether (300 ml). Hydrogen chloride gas was bubbled through thesolution for 5 minutes, until the pH was acidic as shown by pH paper.The mixture was stirred for 15 minutes and the white precipitate wascollected by filtration, washed with three 50 ml portions ofdiethylether and dried under vacuum. The yield of theNHClMe(C₁₈₋₂₂H₃₇₋₄₅)₂ was 12.6 gram.

Preparation of [(p-HOC₆H₄)B(C₆F₅)₃][NHMe (C₁₈₋₂₂H₃₇₋₄₅)₂]

NHClMe(C₁₈₋₂₂H₃₇₋₄₅)₂ (4.58 gram, 8 mmol) was dissolved indichloromethane (50 ml). Trimethylammoniumtris(pentafluorophenyl)(4-hydroxyphenyl)borate[(p-HOC₆H₄)B(C₆F₅)₃][NHEt₃] (5.66 gram, 8 mmol, prepared assubstantially described in Example 1B of U.S. patent application Ser.No. 08/610,647, filed Mar. 4, 1996 (corresponding to WO-96/28480)) wasadded followed by 40 ml distilled water. The mixture was rapidlyagitated for 4 hours and then the water layer was removed by syringe.The dichloromethane layer was washed three times with 40 ml portions ofdistilled water. The dichloromethane layer was then dried over sodiumsulphate, filtered and vacuum dried to yield an oil. The oil wasextracted into toluene (200 ml), the resulting solution was filtered andthe filtrate was vacuum dried to yield 8.84 gram of a colorless oil.

Example 1

Preparation of Catalyst

1 ml of a 0.031M solution of [(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂]in toluene was treated with 18 ml of n-hexane by adding the n-hexaneyielding a cloudy suspension which was stirred for 5 minutes. A solutionof titanium,(N-1,1-dimethylethyl)dimethyl(1-(1,2,3,4,5-eta)-2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)silanaminato))(2-)N)-(η⁴-1,3-pentadiene)(C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (0.33 ml of a 0.0925 M solutionin Isopar™ E; Isopar™ E, a trademark of Exxon Chemical Company, is amixture of C₈ saturated hydrocarbons) was added to generate a red-browncolored suspension. After 5 minutes while stirring a 6 ml aliquot ofthis mixture was treated with 0.2 mmol of triethylaluminum (2 ml of a0.1 M solution in n-hexane) and the mixture was stirred for a further 15minutes before using as such in a polymerization reaction.

Slurry Phase Polymerization

A stirred 5 liter reactor was charged with 100 μmol oftriisobutylaluminum, 3 liters of hexane and 0.5 normal liter of hydrogenbefore heating to 60° C. Ethylene was then added to the reactor in anamount sufficient to bring the total pressure to 10 bar. An aliquot ofthe catalyst prepared as described above containing 10 μmol of titaniumwas then added to initiate the polymerization. The reactor pressure waskept essentially constant by continually feeding ethylene on demandduring the polymerization reaction. The temperature was keptsubstantially constant by cooling the reactor as required. After 49minutes the ethylene feed was shut off and the contents of the reactorwere transferred to a sample pan. After drying, 925 g of a free flowingpolyethylene powder was obtained. The efficiency was calculated to be1,931,100 g polyethylene PE/g Ti and the bulk density 0.29 g/cm³.Scanning electron micrographs of the polymer powder indicated thepresence of spherical particles having a smooth surface morphology.

Example 2 (Comparative)

The slurry polymerization procedure of Example 1 was repeated, yetwithout using triethylaluminum in the catalyst preparation step, withoutadding triisobutylaluminium to the reactor, and while using an amount of30 μmol of titanium for the polymerization reaction. No polyethyleneproduct was obtained.

Example 3

1 ml of a 0.031 M solution of [(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂]in toluene was treated with 10 ml of n-hexane yielding a cloudysuspension and the mixture was stirred for 5 minutes. A mixture of asolution of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (0.33 ml of a0.0925 M solution in Isopar™ E) and 0.3 mmol of triethylaluminum (3 mlof a 0.1 M solution in n-hexane) was added and the mixture was stirredfor 15 minutes. An aliquot of this mixture containing 10 micromol oftitanium was used as such in a polymerization reaction.

The polymerization conditions were identical to those of Example 1except that the duration was 48 minutes. After drying, 850 gram of afree flowing polyethylene powder was obtained. The efficiency wascalculated to be 1,774,530 g PE/g Ti.

Example 4

0.5 ml of a 0.031 M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was treated with 5ml of n-hexane yielding a cloudy suspension and the mixture was stirredfor 5 minutes. 0.075 mmol of triethylaluminum (0.75 ml of a 0.1 Msolution in n-hexane) was added and the mixture was stirred for 5minutes. A solution of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (0.16 mlof a 0.0925 M solution in Isopar™ E) was added and the mixture stirredfor 5 minutes. This mixture was used as such in a polymerizationreaction.

The polymerization conditions were identical to those of Example 1except that the duration was 30 minutes. After drying, 630 gram of afree flowing polyethylene powder was obtained. The efficiency wascalculated to be 888,675 g PE/g Ti.

Example 5

40 gram of silica SP12 (Grace Davison) which had been heated at 250° C.for 3 hours under vacuum was slurried in toluene (400 ml) and thentreated with 40 ml of triethylaluminum in 250 ml toluene. The mixturewas stirred for 1 hour, filtered and the treated silica was washed withtoluene (100 ml, of about 100° C.) and dried under high vacuum.

10 ml of a 0.031 M solution of [(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂]in toluene was treated with 40 ml of n-hexane yielding a cloudysuspension. The mixture was stirred for 5 minutes. 3.1 mmol oftriethylaluminum (15.5 ml of a 0.2 M solution in n-hexane) was added andthe mixture was stirred for 5 minutes. An aliquot of this suspensioncontaining 40 μmole of the borate was treated with 40 μmole of asolution of (C₅Me₄SiMe₂ N^(t)Bu)Ti(η⁴-1,3-pentadiene) (0.43 ml of a0.0925 M solution in Isopar™ E). The resulting suspension was added to aslurry of 1 gram of the silica treated as described above, in 20 ml ofhexane. The mixture was stirred for 5 minutes and then an aliquot of themixture containing 15 μmole of titanium was used as such in a slurrypolymerization.

The polymerization conditions were identical to those of Example 1except that the polymerization time was 30 minutes. 600 grams of a freeflowing polyethylene powder was isolated of bulk density 0.31 g/cm³. Theefficiency was calculated to be 835,070 g PE/g Ti.

Example 6

2 gram of triethylaluminum treated silica (prepared as in Example 5)were placed in a 20 ml flask. In a separate vessel 1.23 ml of a solutionof [(p-HO—C₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] (0.065 M) in toluenecontaining 80 micromol of the borate was diluted with a further 1 ml oftoluene. 0.13 ml of a 0.6 M solution of triethylaluminum in hexane wasadded and the mixture stirred for 10 minutes.

The borate/TEA solution, the volume of which about corresponded to thepore volume of the support material, was added to the treated supportmaterial and the mixture agitated. 8 ml of hexane was added to the drypowder to give a slurry followed by a solution of(C₅Me₅SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (0.86 ml of a 0.0925M solutionin Isopar™ E) to yield a green colored supported catalyst.

The polymerization conditions were identical to those of Example 1except that the polymerization time was 36 minutes and an aliquot ofcatalyst containing 15 micromol Ti was used. 260 gram of free flowingpolymer powder of bulk density 0.25 g/cm³ was obtained. The efficiencywas 361,860 g PE/g Ti.

Example 7

1 ml of a 0.031M solution of [(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂]in toluene was treated with 10 ml of n-hexane to yield a cloudysuspension. In a separate vessel 0.33 ml of a 0.08M solution of(n-BuCp)₂ZrCl₂ in toluene was treated with 3 ml of a 0.1M solution oftriethylaluminum in n-hexane followed by 2 ml of n-hexane. Thezirconocene solution was added to the borate suspension and the mixtureagitated for a few minutes. An aliquot of the catalyst prepared as abovecontaining 10 μmol of zirconium was used in a polymerization reaction.580 g of a free flowing polyethylene powder was obtained after 55minutes. The efficiency was calculated to be 317,912 g PE/g Zr.

Example 8

0.43 ml of a 0.092M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was treated with0.40 ml of a 0.1M solution of triethylaluminum in toluene. 10 ml ofn-hexane was added to yield a fine precipitate. 0.31 ml of a 0.13Msolution of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) in Isopar™ E wasadded and the mixture agitated for a few minutes. An aliquot of thecatalyst containing 20 μmol of titanium was used in a polymerizationreaction. No alkylaluminum scavenger was used and 0.3 liter of hydrogenwas added. 420 g of a free flowing polyethylene powder was obtainedafter 30 minutes. The bulk density was 0.22 g/cm3 and the efficiency wascalculated to be 438,413 PE/g Ti.

Example 9

0.43 ml of a 0.092M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was treated with 10ml of n-hexane to give a cloudy suspension. 0.31 ml of a 0.13M solutionof (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) in Isopar™ E was added toyield an orange-brown colored suspension. An aliquot of this suspensioncontaining 20 μmol Ti was used in a polymerization reaction. 500 μmol oftriethylaluminum was added as a preload to the reactor. 120 g of a freeflowing polyethylene powder was obtained after 15 minutes. Theefficiency was calculated to be 125,260 g PE/g Ti.

Example 10

1 gram of triethylaluminum treated silica (prepared as in Example 5 butusing a 45 micron silica gel, Grace Davison) were placed in a 20 mlflask. In a separate vessel, 0.43 ml of a solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was treated with0.40 ml of a 0.1M solution of triethylaluminum in toluene. The resultingsolution was added to the treated support material and the mixtureagitated. 10 ml of n-hexane was added to slurry the support followed bya solution of 0.031 g ofrac-Me₂Si(2-methyl-4-phenyl-indenyl)₂Zr(1,4-diphenyl-1,3-butadiene) in10 ml of n-hexane.

A stirred 5 liter reactor was charged with 1.6 liters of n-hexane and1.4 liters of propylene and the mixture was maintained at a temperatureof 10° C. An aliquot of the catalyst prepared as above containing 20μmol of Zr was injected into the reactor along with 400 ml of n-hexane.The reactor contents were heated to 70° C. and after holding at 70° C.for ten minutes the reaction was stopped by transferring the contents toa sample container. After drying 585 g of free flowing polypropylenepowder was obtained of bulk density 0.34 g/cm³. The efficiency wascalculated to be 320,723 g PE/g Zr.

Example 11

20 gram of triethylaluminum treated silica (prepared as in Example 5)was charged to a vessel. 17.2 ml of a 0.0465M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was treated with 8ml of a 0.1M solution of triethylaluminum in toluene and the mixturebriefly stirred. A further 10 ml of toluene was added to give a totalvolume of 36 ml. This solution was added to the dry triethylaluminumtreated silica and the mixture was rapidly agitated. 400 ml of n-hexanewas added and the resulting slurry agitated for 10 minutes. 6.15 ml of a0.13M solution of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) in Isopar™ Ewas added and the mixture agitated for 1 hour. This resulted in theformation of a dark green colored supported catalyst.

Isopentane, ethylene, 1-butene (if required), hydrogen and supportedcatalyst were continuously fed into a 10 liter jacketed, continuouslystirred tank reactor and the slurry product formed was continuouslyremoved. The total pressure was 15 bar and the temperature wasmaintained at 70° C. The slurry withdrawn was fed to a flash tank toremove the diluent and the dry, flee-flowing polymer powder wascollected. In a first run the following feed rates were employed.Isopentane (2500 g/hr), ethylene (760 g/hr), hydrogen (1 Nl/hr) andsupported catalyst 0.368 g/hr. Polymer powder was produced at anefficiency of 823,000 g PE/g Ti and with the following properties. I22.41, density 0.9638 g/cm3. In a second run the following feed rateswere employed. Isopentane (2500 g/hr), ethylene (1120 g/hr), 1-butene(37 g/hr), hydrogen (1 Nl/hr) and supported catalyst (0.325 g/hr).Polymer powder was produced at all efficiency of 1,569,000 g PE/g Ti andwith the following properties, I₂ 1.02, density 0.9303 g/cm³, 1-butene1.72 percent.

Example 12

15 gram of triethylaluminum treated silica (prepared as in Example 5 butusing a 45 micron particle size silica gel, Grace Davison) was chargedto a vessel. 2 ml of a 0.298M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was treated with 6ml of a 0.1M solution of triethylaluminum in toluene and the mixturebriefly stirred. A further 8.5 ml of toluene was added to give a totalvolume of 16.5 ml. This solution was added to the dry triethylaluminumtreated silica and the mixture was rapidly agitated. 400 ml of n-hexanewas added and the resulting slurry agitated for 10 minutes. 4.61 ml of a0.13M solution of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) in Isopar™ Ewas added and the mixture agitated for 1 hour. This resulted in theformation of a dark green colored supported catalyst.

n-Hexane (2500 g/hr), ethylene (1025 g/hr), hydrogen (3.5 Nl/hr) andsupported catalyst (0.5875 g/hr) were continuously fed to a 10 liter,jacketed continuously stirred tank reactor. The total pressure was 12bar and the temperature was maintained at 65° C. The slurry withdrawnwas fed to a second identical reactor along with n-hexane (2500 g/hr),ethylene (950 g/hr), 1-butene (4.7 g/hr) and supported catalyst (0.5875g/hr). The total pressure in the second reactor was 11 bar and thetemperature 75° C. The slurry withdrawn was fed to a flash tank toremove the diluent and the dry, free flowing powder polymer powder wascollected. The overall efficiency was calculated to be 750,000 g PE/gTi. The polymer powder had the following properties. I₂ 0.47, density0.9679 g/cm³ and bulk density 0.373 g/cm³.

Scanning Electron Micrographs: Samples of slurry produced polyethylene(HDPE), from Example 1, which had been gold coated were examined byscanning electron micrograph using a Philips model SEM505 operating atan accelerating voltage of 6 kV, with results as shown in FIG. 1A andFIG. 1B at a magnification of 50 times, FIG. 2A and FIG. 2B at 200times, and FIG. 3A and FIG. 3B at 1000 times. The photomicrographsindicate that the surface morphology is very smooth and that thereappear to be particles of primarily two size ranges. The largerparticles are in the size range of approximately 50 microns in diameterand the smaller particles are in the size range of approximately 5microns in diameter.

Gas Phase Examples

The polymerization examples which follow were carried out in a 13 litergas phase reactor having a four inch diameter thirty inch longfluidization zone and an eight inch diameter ten inch long velocityreduction zone which are connected by a transition section havingtapered walls. Typical operating ranges were 40 to 100° C., 6 to 25 bartotal pressure and up to 8 hours reaction time. Ethylene, comonomer,hydrogen and nitrogen entered the bottom of the reactor where theypassed through a gas distributor plate. The flow of the gas was 2 to 8times the minimum particle fluidization velocity. See FluidizationEngineering, 2nd Ed., D. Kunii and O. Levenspiel, 1991Butterworth-Heinemann. Most of the suspended solids disengaged in thevelocity reduction zone. The reactant gases exited the top of thevelocity reduction zone and passed through a dust filter to remove anyfines. The gases then passed through a gas booster pump. The polymer wasallowed to accumulate in the reactor over the course of the reaction.The total system pressure was kept constant during the reaction byregulating the flow of monomer into the reactor. Polymer was removedfrom the reactor to a recovery vessel by opening a valve located at thebottom of the fluidization zone. The polymer recovery vessel was kept ata lower pressure than the reactor. The pressures of ethylene, comonomerand hydrogen reported refer to partial pressures.

The mode of reactor operation which was employed is referred to assemi-batch. The catalyst was prepared and loaded into a catalystinjector in an inert atmosphere glovebox. The injector was removed fromthe glovebox and inserted into the tope of the reactor. Appropriateamounts of ethylene, 1-butene, hydrogen and nitrogen were introducedinto the reactor to bring the total pressure to the desired reactiontemperature. The catalyst was then injected and the polymer was usuallyallowed to form for 30 to 90 minutes. The total system pressure was keptconstant during the reaction by regulating the flow of monomer into thereactor. Upon completion of the run the reactor was emptied and thepolymer powder was collected.

Example 13

Catalyst/support Preparation

15.9 grams of Crosfield type ES70Y silica (surface area=315 m²/g and aMalvern particle size [D50]=106.8 micron) was heated at 500° C. for 4hours in an inert stream of nitrogen. The silica was allowed to cool toroom temperature in an inert stream of nitrogen. The silica calcinationtube was then sealed at both ends and brought into an inert atmosphereglovebox. The silica was removed from the calcination tube then slurriedwith 80 ml of hexane at a ratio of 5 ml hexane/gram silica. To theslurried silica was added 2.93 grams of a 93 weight percent solution oftriethylaluminum (TEA) which corresponded to a treatment of 1.5 mmolesTEA/gram silica. The slurry was allowed to sit for 2 hours with gentleagitation by hand every 15 to 20 minutes. After 2 hours the silica wasfiltered and washed twice with a total of 100 ml of hexane to remove anysoluble aluminum compounds which may have resulted during the TEAtreatment step. The silica was then dried at room temperature undervacuum to give a free-flowing powder.

To 100 ml of a 0.036 M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was added 0.0036moles (0.383 grams) of TEA. The mixture was stirred at room temperaturefor 18½ hours. 0.278 ml of the preceding solution was added dropwise to1.0 gram of the TEA treated ES70Y silica described previously followedby vigorous shaking for 15 minutes. 0.0427 ml of a 0.234 M solution of(η⁵-C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) was then added dropwise tothe silica followed by vigorous shaking for 15 minutes. The catalystloading was 10 micromol/gram silica. To the formulated catalyst wasadded 10 ml of hexane followed by vigorous shaking of the resultingslurry for 20 minutes. The slurry was then filtered and washed twicewith a total of 10 ml of hexane. The formulated catalyst was then driedat room temperature under vacuum to give a free-flowing powder.

Polymerization

0.1 grams of the formulated catalyst described above was added to thesemi-batch gas phase reactor which was under an ethylene pressure of 6.5bar, a 1-butene pressure of 0.14 bar, a hydrogen pressure of 0.04 barand a nitrogen pressure of 2.8 bar. The temperature of polymerizationthroughout the run was 70° C. A 6° C. exotherm was measured uponinjection of the catalyst. 16.0 grams of polymer were recovered after 30minutes.

Example 14

0.075 grams of the formulated catalyst described in Example 13 was addedto the semi-batch gas phase reactor which was under an ethylene pressureof 6.5 bar, a 1-butene pressure of 0.14 bar, a hydrogen pressure of 0.04bar and a nitrogen pressure of 2.8 bar. The temperature ofpolymerization throughout the run was 70° C. A 6° C. exotherm wasmeasured upon injection of the catalyst. 15.9 grams of polymer wererecovered after 30 minutes.

Example 15

0.05 grams of the formulated catalyst described in Example 13 was mixedwith 0.415 grams of the TEA treated silica described in Example 13. Themixture was added to the semi-batch gas phase reactor which was under anethylene pressure of 6.5 bar, a 1-butene pressure of 0.14 bar, ahydrogen pressure of 0.04 bar and a nitrogen pressure of 2.8 bar. Thetemperature of polymerization throughout the run was 69° C. A 5° C.exotherm was measured upon injection of the catalyst. 5.4 grams ofpolymer were recovered after 18 minutes.

Example 16

0.05 grams of the formulated catalyst described in Example 13 was mixedwith 0.4 grams of the TEA treated silica described in Example 13. Themixture was added to the semi-batch gas phase reactor which was under anethylene pressure of 6.5 bar, a 1-butene pressure of 0.14 bar, ahydrogen pressure of 0.04 bar and a nitrogen pressure of 13.7 bar. Thecatalyst was injected at a reactor temperature of 70° C. A 4° C.exotherm was measured upon injection of the catalyst. Followinginjection of the catalyst the temperature in the reactor rose to 75° C.over the course of 90 minutes. 24.3 grams of polymer were recoveredafter 90 minutes.

Example 17

Catalyst Preparation

To 100 ml of a 0.036 M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was added 0.0036moles (0.383 grams) of TEA. The mixture was allowed to stir at roomtemperature for 18½ hours. 0.417 ml of the preceding solution was addeddropwise to 1.0 gram of the TEA treated ES70Y silica describedpreviously in Example 13 followed by vigorous shaking for 15 minutes.0.0641 ml of a 0.234 M solution of(η⁵C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) was then added dropwise tothe silica followed by vigorous shaking for 15 minutes. The catalystloading was 15 micromol/gram silica. To the formulated catalyst wasadded 10 ml of hexane followed by vigorous shaking of the resultingslurry for 20 minutes. The slurry was then filtered and washed twicewith a total of 10 ml of hexane. The formulated catalyst was then driedat room temperature under vacuum to give a free-flowing powder.

Polymerization

0.033 grams of the formulated catalyst described above was mixed with0.35 grams of the TEA treated silica described in Example 13. Themixture was added to the semi-batch gas phase reactor which was under anethylene pressure of 6.5 bar a 1-butene pressure of 0.14 bar and anitrogen pressure of 13.7 bar. The temperature of polymerizationthroughout the run was 72° C. No exotherm was measured upon injection ofthe catalyst. 5.8 grams of polymer were recovered after 15 minutes.

Example 18

0.017 grams of the formulated catalyst described in Example 5 was mixedwith 0.35 grams of the TEA treated silica described in Example 1. Themixture was added to the semi-batch gas phase reactor which was under anethylene pressure of 6.5 bar, a 1-butene pressure of 0.14 bar, ahydrogen pressure of 0.04 bar and a nitrogen pressure of 13.7 bar. Thecatalyst was injected at a reactor temperature of 71° C. No exotherm wasmeasured upon injection of the catalyst. 12.5 grams of polymer wererecovered after 90 minutes.

Example 19

Catalyst Preparation

To 100 ml of a 0.036 M solution of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene was addled 0.0036moles (0.383 grams) of TEA. The mixture was allowed to stir at roomtemperature for 18½ hours. 0.278 ml of the preceding solution was addeddropwise to 1.0 gram of a TEA treated Crosfield type ES70 silica(surface area=289 m²/g and a Malvern particle size [D50]=35.2 micron)followed by vigorous shaking for 15 minutes. The Crosfield type ES70silica had been calcined and treated with TEA in a manner analogous tothe procedure described in Example 1. 0.0427 ml of a 0.234 M solution of(η⁵C₅Me₄SiMe₂N^(t)Bu)—Ti(η⁴-1,3-pentadiene) was then added dropwise tothe silica followed by vigorous shaking for 15 minutes. The catalystloading was 10 mmol/gram silica. To the formulated catalyst was added 10ml of hexane followed by vigorous shaking of the resulting slurry for 20minutes. The slurry was then filtered and washed twice with a total of10 ml of hexane. The formulated catalyst was then dried at roomtemperature under vacuum to give a free-flowing powder.

Polymerization

0.05 grams of the formulated catalyst described above was mixed with0.35 grams of the TEA treated silica described in Example 13. Themixture was added to the semi-batch gas phase reactor which was under anethylene pressure of 6.5 bar, a 1-butene pressure of 0.14 bar, ahydrogen pressure of 0.04 bar and a nitrogen pressure of 13.7 bar. Thetemperature of polymerization throughout the run was 72° C. A 3° C.exotherm was measured upon injection of the catalyst. 26.3 grams ofpolymer were recovered after 90 minutes.

III. Polypropylene Examples Example 20

Catalyst Preparation

Regarding various aspects of the preparation of the transition metalcompound, See Organomet 13, (1994), 954 at page 962; see also U.S. Pat.No. 5,278,264 hereby incorporated herein by reference:

rac-Me₂Si(2-methyl-4-phenyl-indenyl)₂ZrCl₂ (4.00 g, 6.36 mmol) and diene(1.312 g, 6.36 mmol) were weighed into a 250 mL flask and slurried into150 mL of octane. 8.9 mL of nBuLi (1.6 M, 14.31 mmol) was added viasyringe. The reaction mixture was stirred at room temperature over theweekend. The reaction was then held at 80-85° C. for approximately 6hours followed by 2 hours at reflux, then cooled to room temperature.The octane solution was filtered after cooling and the insolubles werewashed with hexane until colorless. The solvent was removed in vacuo.The product was slurried into 10 ml fresh hexane and placed in thefreezer at −30° F. for 1 hour. The cold slurry was filtered and thesolid product dried in vacuo, givingrac-Me₂Si(2-methyl-4-phenyl-indenyl)₂Zr(1,4-diphenyl-1,3-butadiene) as ared solid (yield=2.182 g, 45 percent; 82.3 weight percent 24DN, 17.7weight percent free diene). 1H NMR (C₆D₆, ppm): 7.8-6.5 (multiplets,aromatic protons, and free diene protons), 5.6 (s, 2H, indenyl proton),3.45 (multiplet, 2H, PhC4H4Ph) 1.7 (singlet overlapping multiplet, s,indenyl methyl; m, PhC₄H₄Ph, total 811), 0.9 (s, SiMe₂, 6H).

Pretreatment of the silica: To 5.00 g 50 μm silica (Grace DavisonXPO-2402, which had previously been calcined at 500° C.) was added 50 mLtoluene. To the mixture, 5 mL of neat triethylaluminum (TEA) were added,and the mixture was stirred for one hour. The mixture was filtered overa medium frit, and the silica was washed twice with 50 mL boilingtoluene, followed by 50 mL hexane. The silica was then pumped dry byclosure of the frit top with a stopper. After 3 hours 45 minutes invacuo, 5.48 g of treated silica (SiO₂/TEA) was recovered.

A solution of 0.91 mL of 0.1 M of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene (91 μmoles) wascombined with 2.7 mL of toluene and 0.91 mL of 0.1 M triethylaluminum(TEA, 91 μmoles) and the solution with a total volume of 4.5 mL wasstirred for 10 minutes. This solution was added in three portions to2.28 g of the pretreated SiO₂ prepared above in a 50 mL flask. Themixture was gently mixed for several minutes with a spatula to evenlydistribute the liquid over the solid until a free flowing powder wasobtained. 20 mL of hexane was added to the solid, mixing the new mixturewith a spatula for 2 minutes. The pretreated silica was filtered andpumped dry for one hour. 2.33 g solid product was obtained and placed ina 100 mL vessel. A solution of 85 mg of 24Dn transition metal compoundprepared above was dissolved in 3.6 mL of toluene (91 μmoles) and addedto the vessel in 3 portions of about 1.2 mL each, gently mixingthoroughly after each portion had been added with a spatula to ensurehomogeneous distribution of the catalyst solution on the solid. Thesolid material was rinsed four times with 40 mL hexane. The grayish-bluesolid was dried in vacuo one hour. A sample of 127 mg of this finishedmaterial was submitted for Zr analysis by neutro activation. Theanalysis showed that the loading was 23 μmoles of Zr/g silica.

Example 21

Preparation of the pretreated support. Crosfield silica ES70 wascalcined at 250° C. for four hours with nitrogen flow through afluidized bed. After cooling, to 5 g of the calcined silica in a 4 ozbottle were added 50 mL hexane and 5 mL of neat TEA. The bottle wasclosed and rocked for an hour on a rocker type mixer. The sample wasvacuum dried for one hour to give 5.3 g of finished TEA-treated silica.

A solution of 0.6 mL of 0.1 M of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] in toluene (60 μmoles) wascombined with 0.3 mL of toluene and 0.0.6 mL of 0.1 M triethylaluminum(TEA, 60 μmoles) and the solution with a total volume of 1.5 mL wasstirred for 10 minutes. This solution was added in three portions to 1.0g of the pretreated SiO₂ prepared above in a 100 mL bottle. The mixturewas gently mixed for several minutes with a spatula to evenly distributethe liquid over the solid until a free flowing powder was obtained, atwhich point it was washed three times with 20 mL portions of hexane. Thepretreated silica, was filtered and pumped dry for one hour. The solidproduct was placed in a 100 mL vessel. A 1.5 mL solution containing 60μmoles of 24Dn transition metal compound was added to the vessel, gentlymixing thoroughly with a spatula to ensure homogeneous distribution ofthe catalyst solution on the solid.

General Polymerization Procedure

Propylene, Isopar™ E, hydrogen, hexane and nitrogen were all purified bypassage through packed columns of activated Q-5 and alumina. Thesupported 24Dn catalyst was slurried in the glove box with about 20 mLof hexane.

Polypropylene Prepared With Supported Catalyst from Example 20

A two-liter stainless steel reactor was dried by vigorous stirring of 1ml 0.1 M triisobutyl aluminum solution in toluene added to 1 literIsopar™ for one hour at 70° C. The reactor was washed with Isopar™ at70° C. It was then charged with a mixture consisting of 351 g ofpropylene, 40 g of hexane, and 26 delta psi hydrogen by differentialpressure expansion from a 75 mL tank.

The mixture was heated to 70° C. and then a slurry prepared with 100 mg(2 μmoles 24Dn catalyst as Zr), 10 μmoles TEA and 5 ml hexane was addedto the reactor. The reaction was allowed to proceed for 30 minutes. Thecontents of the reactor were then collected in a nitrogen purgedstainless steel container. The polymers were dried overnight in a vacuumoven at 130° C. Yield 48 g. Standard 13C techniques showed that thepolymer was 96 percent triad [mm] isotactic, with 0.95 percent inverseinsertions. The polymer had Mw/Mn=320,000/82.000=3.9, as determined bystandard GPC techniques.

Polypropylene Prepared With Supported Catalyst from Example 21

Same procedure as described above was repeated, using 351 g ofpropylene, 40 g of hexane, and 26 delta psi hydrogen by differentialpressure expansion from a 75 ml tank. After 35 minutes of reaction time,the polymer was collected and dried as described above. The yield ofpolypropylene was 45 g.

Solubility of Ionic Compounds Solubility at 22° C. Solubility at 22° C.Compound Note Solvent mol/liter weight percent[NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂][HOC₆H₄B(C₆F₅)₃] 1 toluene >0.3 >28.2[NEt₃H][HOC₆H₄B(C₆F₅)₃] 2 toluene <0.001 <0.08[NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂][HOC₆H₄B(C₆F₅)₃] 3 n-hexane 0.014 2.37[NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂][B(C₆F₅)₄] 4 n-hexane >0.34 >38.8[NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂][HOC₆H₄B(C₆F₅)₃] + TEA 5 toluene >0.3 >28[NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂][HOC₆H₄B(C₆F₅)₃] + TEA 6 n-hexane 0.0024 0.45 1)The influence of the long hydrocarbon chain ammonium cation on thetoluene solubility of the hydroxyborate anion is evidenced by comparing1 and 2. 2) The hexane solubility of[(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂] is much less than the toluenesolubility (compare 1 and 3). 3) The influence of the hydroxysubstituent on the solubilities of the long chain ammonium salts isevidenced by comparing 3 and 4. 4) The influence of solvent on thesolubilities of the product of [(p-HOC₆H₄)B(C₆F₅)₃][NHMe(C₁₈₋₂₂H₃₇₋₄₅)₂]and TEA is evidenced by comparing 5 and 6. Note that 6 is even moreinsoluble than 3.

What is claimed is:
 1. A compound that is the reaction product of: (a)an ionic compound comprising (a)(1) a cation and (a)(2) an anion havingup to 100 nonhydrogen atoms and containing at least one substituentcomprising a moiety having an active hydrogen, wherein the cation (a)(1)is represented by the following general formula: [L*—H]⁺, wherein: L* isa nitrogen, oxygen, sulfur or phosphorus containing Lewis basecontaining from one to three C₁₀₋₄₀ alkyl groups with a total of from 12to 100 carbons, and the anion (a)(2) corresponds to Formula (II):[M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II)  wherein: M′ is a metal ormetalloid selected from Groups 5-15 of the Periodic Table of theElements; Q independently in each occurrence is selected from the groupconsisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide,hydrocarbyl, and substituted-hydrocarbyl radicals, includinghalo-substituted hydrocarbyl radicals, and hydrocarbyl- andhalohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbylportion in each of these groups preferably having from 1 to 20 carbons,with the proviso that in not more than one occurrence is Q halide; G isa polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and rgroups (T—H); the group (T—H) is a radical wherein T comprises O, S, NR,or PR, the O, S, N or P atom of which is bonded to hydrogen atom Hwherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, atrihydrocarbyl germyl radical or hydrogen; m is an integer from 1 to 7;n is an integer from 0 to 7; q is an integer of 0 or 1; r is an integerfrom 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 7;and n+z−m=d, and (c) an organometal or metalloid compound correspondingto the formula: M^(o)R^(c) _(x)X^(a) _(y),  wherein M^(o) is a metal ormetalloid selected from Groups 2, 12, 13 or 14 of the Periodic Table ofthe Elements, R^(c) independently each occurrence is hydrogen or a grouphaving from 1 to 80 nonhydrogen atoms which is hydrocarbyl,hydrocarbylsilyl, trihydrocarbylsilyl, trihydrocarbylgermyl orhydrocarbylsilylhydrocarbyl; X^(a) is a noninterfering group having from1 to 100 nonhydrogen atoms which is halo-substituted hydrocarbyl,hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy orhalide; x is a nonzero integer which may range from 1 to an integerequal to the valence of M^(o); y is zero or a nonzero integer which mayrange from 1 to an integer equal to 1 less than the valence of M^(o);and x+y equals the valence of M^(o).
 2. The catalyst componentdispersion of claim 1, wherein the catalyst component further comprises(b) a transition metal compound and wherein the catalyst component is asubstantially inactive catalyst percursor; or wherein the catalystcomponent further comprises (c) an organometal or metalloid compoundwherein the metal or metalloid is selected from the Groups 1-14 of thePeriodic Table of the Elements and the catalyst component is a reactionproduct of (a) and (c).
 3. The catalyst component dispersion of claim 1,characterized by an average particle size of (a), as measured by laserdiffraction, in the range of from 0.1 to 200 μm.
 4. The catalystcomponent dispersion of claim 1, wherein the anion (a)(2) corresponds toFormula (II): [M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II) wherein: M′is a metal or metalloid selected from Groups 5-15 of the Periodic Tableof the Elements; Q independently in each occurrence is selected from thegroup consisting of hydride, dihydrocarbylaimdo, halide,hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals,including halo-substituted hydrocarbyl radicals, and hydrocarbyl- andhalohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbylportion in each of these groups preferably having from 1 to 20 carbons,with the proviso that in not more than one occurrence is Q halide; G isa polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and rgroups (T—H); the group (T—H) is a radical wherein T comprises O, S, NR,or PR, the O, S, N or P atom of which is bonded to hydrogen atom Hwherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, atrihydrocarbyl germyl radical or hydrogen; m is an integer from 1 to 7;n is an integer from 0 to 7; q is an integer of 0 or 1; r is an integerfrom 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 7;and n+z−m=d.
 5. The catalyst component dispersion of claim 4, wherein inthe anion (a)(2) the at least one substituent comprising a moiety havingan active hydrogen corresponds to Formula (I): G_(q)(T—H)_(r)  (I)wherein G is a polyvalent hydrocarbon radical, the group (T—H) is aradical wherein T comprises O, S, NR, or PR, the O, S, N, or P atom ofwhich is bonded to hydrogen atom H, wherein R is a hydrocarbyl radical,a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical orhydrogen, H is hydrogen, q is 0 or 1, and r is an integer from 1 to 3.6. The catalyst component dispersion of claim 1, wherein the cation(a)(1) is selected from the group consisting of Bronsted acidic cations,carbonium cations, silylium cations, oxonium cations, organometalliccations and cationic oxidizing agents.
 7. The catalyst componentdispersion of claim 6, wherein the cation (a)(1) of ionic compound (a)is represented by the following general formula: [L*—H]⁺, wherein: L* isa nitrogen, oxygen, sulfur or phosphorus containing Lewis basecontaining from one to three C₁₀₋₄₀ alkyl groups with a total of from 12to 100 carbons.
 8. The catalyst component dispersion of claim 7, whereinthe cation (a)(1) of ionic compound (a) is represented by the followinggeneral formula: [L*—H]⁺, wherein: L* is a nitrogen, oxygen, sulfur orphosphorus containing Lewis base containing from one to three C₁₀₋₄₀alkyl groups with a total of from 12 to 100 carbons, and the anion(a)(2) is tris(pentafluorophenyl)(4-hydroxyphenyl)borate.
 9. Thecatalyst component dispersion of claim 1 in dry particulate formproduced by removal of the diluent.
 10. A supported solid catalystcomprising (a) an ionic compound comprising (a)(1) a cation and (a)(2)an anion having up to 100 nonhydrogen atoms and the anion containing atleast one substituent comprising a moiety having an active hydrogen, (b)a transition metal compound, (c) an organometal or metalloid compoundwherein the metal or metalloid is selected from the Groups 1-14 of thePeriodic Table of the Elements, and (d) a support material, wherein, (i)the support material is a pretreated support material and in thesupported catalyst component the anion (a)(2) is not chemically bondedto the support (d), or (ii) the ionic compound has a solubility intoluene at 22° C. of at least 0.1 weight percent, the support materialused is a support material containing tethering groups and in thesupported catalyst component the anion (a)(2) is chemically bonded tothe support (d); and, wherein the solid catalyst is obtained bycombining components (a), (b), (c), and (d) in any order, and wherein,during at least one step in the preparation of the solid catalyst,component (a) is dissolved in a diluent in which (a) is soluble,optionally in the presence of one or more of components (b), (c), and(d) or the contact product of (a) with such one or more of (b), (c), and(d), and then is converted into solid form.
 11. The supported solidcatalyst of claim 10, wherein, during the preparation of the solidcatalyst, a dispersion comprising component (a) is generated by coolinga solution of (a) in a diluent in which (a) is soluble, by contacting asolution of (a) in a diluent in which (a) is soluble with a diluent inwhich (a) is insoluble or sparingly soluble, by evaporating diluent froma solution of (a), by adding one or more precipitating agents to asolution of (a), or a combination of two or more of these techniques.12. The supported solid catalyst of claim 11 wherein, during thepreparation of the solid catalyst, a dispersion comprising component (a)in solid form is generated by contacting a solution of (a) in a diluentin which (a) is soluble, optionally in the presence of one or more ofcomponents (b), (c), and (d) or the contact product of (a) with one ormore of (b), (c), and (d), with a diluent in which (a) is insoluble orsparingly soluble.
 13. The supported solid catalyst of claim 10, whereinthe anion (a)(2) corresponds to Formula (II):[M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II) wherein: M′ is a metal ormetalloid selected from Groups 5-15 of the Periodic Table of theElements; Q independently in each occurrence is selected from the groupconsisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide,hydrocarbyl, and substituted-hydrocarbyl radicals, includinghalo-substituted hydrocarbyl radicals, and hydrocarbyl- andhalohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbylportion in each of these groups preferably having from 1 to 20 carbons,with the proviso that in not more than one occurrence is Q halide; G isa polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and rgroups (T—H); the group (T—H) is a radical wherein T comprises O, S, NR,or PR, the O, S, N or P atom of which is bonded to hydrogen atom Hwherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, atrihydrocarbyl germyl radical or hydrogen; m is an integer from 1 to 7;n is an integer from 0 to 7; q is an integer of 0 or 1; r is an integerfrom 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 7;and n+z−m=d.
 14. The supported solid catalyst of claim 13, wherein inthe anion (a)(2) the at least one substituent comprising a moiety havingan active hydrogen corresponds to Formula (I): G_(q)(T—H)_(r)  (I)wherein G is a polyvalent hydrocarbon radical, the group (T—H) is aradical wherein T comprises O, S, NR, or PR, the O, S, N, or P atom ofwhich is bonded to hydrogen atom H, wherein R is a hydrocarbyl radical,a trihydrocarbylsilyl radical, a trihydrocarbyl germyl radical orhydrogen, H is hydrogen, q is 0 or 1, and r is an integer from 1 to 3.15. The supported solid catalyst of one of claims 10, wherein the cation(a)(1) is selected from the group consisting of Bronsted acidic cations,carbonium cations, silylium cations, oxonium cations, organometalliccations and cationic oxidizing agents.
 16. The supported solid catalystof claim 15, wherein the cation (a)(1) of ionic compound (a) isrepresented by the following general formula: [L*—H]⁺, wherein: L* is anitrogen, oxygen, sulfur or phosphorus containing Lewis base containingfrom one to three C₁₀₋₄₀ alkyl groups with a total of from 12 to 100carbons.
 17. The supported solid catalyst of claim 16, wherein thecation (a)(1) of ionic compound (a) is represented by the followinggeneral formula: [L*—H]⁺, wherein: L* is a nitrogen, oxygen, sulfur orphosphorus containing Lewis base containing from one to three C₁₀₋₄₀alkyl groups with a total of from 12 to 100 carbons, and the anion(a)(2) is tris(pentafluorophenyl)(4-hydroxyphenyl)borate.
 18. Thesupported solid catalyst of claim 10, wherein the organometal ormetalloid compound corresponds to the formula AlR^(o) _(x), whereinR^(o) independently in each occurrence is hydrogen or a hydrocarbylradical having from 1 to 20 carbon atoms, and x is
 3. 19. A method forpreparing a dispersion of a supported catalyst component comprising (a)an ionic compound comprising (a)(1) a cation and (a)(2) an anion havingup to 100 nonhydrogen atoms and the anion containing at least onesubstituent comprising a moiety having an active hydrogen, and (d) asupport material, where the supported catalyst component is in solidform dispersed in a diluent in which both (a) and (d) are insoluble orsparingly soluble, the method comprising converting a solution of theionic compound (a) in a diluent in which (a) is soluble in the presenceof the support material into a dispersion comprising component (a) insolid form, and wherein, (i) the support material used is a pretreatedsupport material and, in the supported catalyst component, the anion(a)(2) is not chemically bonded to the support (d), or (ii) the ioniccompound used has a solubility in toluene at 22° C. of at least 0.1weight percent, the support material used is a support materialcontaining tethering groups and, in the supported catalyst component,the anion (a)(2) is chemically bonded to the support (d).
 20. The methodof claim 19, wherein the converting is done in the presence of (b) atransition metal compound and wherein the catalyst component is asubstantially inactive catalyst percursor; or wherein the converting isdone in the presence of (c) an organometal or metalloid compound whereinthe metal or metalloid is selected from the Groups 1-14 of the PeriodicTable of the Elements and the catalyst component is a reaction productof (a) and (c).
 21. The method of claim 19, wherein the dispersioncomprising component (a) is generated by cooling a solution of (a) in adiluent in which (a) is soluble, by contacting a solution of (a) in adiluent in which (a) is soluble with a diluent in which (a) is insolubleor sparingly soluble, by evaporating diluent from a solution of (a), byadding one or more precipitating agents to a solution of (a), or acombination of two or more of these techniques.
 22. The method of claim21, wherein the dispersion comprising component (a) is generated bycontacting a solution of (a) in a diluent in which (a) is soluble with adiluent in which (a) is insoluble or sparingly soluble.
 23. The methodof one of claims 22, wherein the diluent in which (a) is soluble isselected from the group consisting of toluene, benzene, and xylenes, andthe diluent in which (a) is insoluble or sparingly soluble is selectedfrom the group consisting of pentane, hexane, heptane, and octane. 24.The method of claim 19, wherein the anion (a)(2) corresponds to Formula(II): [M′^(m+)Q_(n)(G_(q)(T—H)_(r))_(z)]^(d−)  (II) wherein: M′ is ametal or metalloid selected from Groups 5-15 of the Periodic Table ofthe Elements; Q independently in each occurrence is selected from thegroup consisting of hydride, dihydrocarbylamido, halide,hydrocarbyloxide, hydrocarbyl, and substituted-hydrocarbyl radicals,including halo-substituted hydrocarbyl radicals, and hydrocarbyl- andhalohydrocarbyl-substituted organo-metalloid radicals, the hydrocarbylportion in each of these groups preferably having from 1 to 20 carbons,with the proviso that in not more than one occurrence is Q halide; G isa polyvalent hydrocarbon radical having r+1 valencies bonded to M′ and rgroups (T—H); the group (T—H) is a radical wherein T comprises O, S, NR,or PR, the O, S, N or P atom of which is bonded to hydrogen atom Hwherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, atrihydrocarbyl germyl radical or hydrogen; m is an integer from 1 to 7;n is an integer from 0 to 7; q is an integer of 0 or 1; r is an integerfrom 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 7;and n+z−m=d.
 25. The method of claim 24, wherein the cation (a)(1) ofionic compound (a) is represented by the following general formula:[L*—H]⁺, wherein: L* is a nitrogen, oxygen, sulfur or phosphoruscontaining Lewis base containing from one to three C₁₀₋₄₀ alkyl groupswith a total of from 12 to 100 carbons, and the anion (a)(2) istris(pentafluorophenyl)(4-hydroxyphenyl)borate.
 26. The method of claim19 further comprising removal of the diluent to produce the catalystcomponent in dry particulate form.
 27. A method for preparing a solidcatalyst comprising combining, in any order, (a) an ionic compoundcomprising (a)(1) a cation and (a)(2) an anion having up to 100nonhydrogen atoms and the anion containing at least one substituentcomprising a moiety having an active hydrogen, (b) a transition metalcompound, (c) an organometal or metalloid compound wherein the metal ormetalloid is selected from the Groups 1-14 of the Periodic Table of theElements, and (d) a support material, wherein during at least one stepin the preparation of the solid catalyst, component (a) is dissolved ina diluent in which (a) is soluble to produce a solution of (a),optionally in the presence of one or more of components (b), (c), and(d) or the contact product of (a) with such one or more of (b), (c), and(d), and then is converted into solid form, optionally followed byrecovering the solid catalyst in dry particulate form, wherein, (i) thesupport material used is a pretreated support material and in thesupported catalyst the anion (a)(2) is not chemically bonded to thesupport (d), or (ii) the ionic compound used has a solubility in tolueneat 22° C. of at least 0.1 weight percent, the support material used is asupport material containing tethering groups and in the supportedcatalyst the anion (a)(2) is chemically bonded to the support (d). 28.The method of claim 27, wherein the support material used is apretreated support material with a pore volume of from 0.1 to 5 cm³/gand in the supported catalyst the anion (a)(2) is not chemically bondedto the support (d), and wherein the volume of the solution of (a),optionally in the presence of one or both of (b) and (c), is from 20volume percent to 200 volume percent of the total pore volume of thesupport material used.
 29. The method of claim 27, wherein the supportmaterial used is a pretreated support material with a pore volume offrom 0.1 to 5 cm³/g and in the supported catalyst the anion (a)(2) isnot chemically bonded to the support (d), and wherein the volume of thesolution of (a), optionally in the presence of one or both of (b) and(c), is greater than 200 volume percent of the total pore volume of thesupport material used.
 30. The method of one of claims 27, wherein thesolution of (a) is produced in the presence of (b).
 31. The method ofone of claims 27, wherein the solution of (a) is produced in thepresence of (c).
 32. The method of one of claims 27, wherein thesolution of (a) is produced in the presence of (b) and (c).
 33. Themethod of one of claims 27, wherein the solid catalyst is produced byadding the solution of (a), optionally containing one or both of (b) and(c), to substantially dry pretreated support material, followed byremoval of the diluent.
 34. The method of claim 27 wherein during the atleast one step in the preparation of the solid catalyst, a dispersioncomprising component (a) in solid form is generated by cooling asolution of (a) in a diluent in which (a) is soluble, by contacting asolution of (a) in a diluent in which (a) is soluble with a diluent inwhich (a) is insoluble or sparingly soluble, by evaporating diluent froma solution of (a), by adding one or more precipitating agents to asolution of (a), or a combination of two or more of these techniques.35. The method of one of claims 27, wherein component (d) is addedduring one of the steps in the preparation of the solid catalyst. 36.The method of one of claims 27, wherein the diluent in which (a) issoluble is selected from the group consisting of toluene, benzene, andxylenes, and the diluent in which (a) is insoluble or sparingly solubleis selected from the group consisting of pentane, hexane, heptane, andoctane.
 37. A method for activating a substantially inactive catalystprecursor to form a catalyst suitable for addition polymerizationwherein a substantially inactive catalyst precursor comprising (a) anionic compound comprising (a)(1) a cation and (a)(2) an anion having upto 100 nonhydrogen atoms and the anion containing at least onesubstituent comprising a moiety having an active hydrogen, (b) atransition metal compound, and (d) a support material, is contacted with(c) an organometal or metalloid compound, where the metal or metalloidis selected from Groups 1-14 of the Periodic Table of the Elements, toform an active catalyst.
 38. The method of claim 37 wherein one or moreof (a),(b) and (d), and the organometal or metalloid compound (c) areseparately added into an addition polymerization reactor containingaddition polymerizable monomer or monomers.
 39. The method of claim 37wherein a dispersion of a solid substantially inactive catalystprecursor, comprising (a),(b) and (d), and the organometal or metalloidcompound (c) are each separately added into an addition polymerizationreactor containing addition polymerizable monomer or monomers.
 40. Themethod of one of claims 37, wherein the addition polymerization reactoris operated under slurry phase or gas phase polymerization conditions.41. The method of claim 40, wherein the addition polymerization reactoris operated under slurry phase polymerization conditions.
 42. The methodof claim 40, wherein the addition polymerization reactor is operatedunder gas phase polymerization conditions.
 43. The method of claim 37,wherein the organometal or metalloid compound (c) corresponds to theformula: M^(o)R^(c) _(x)X^(a) _(y), wherein M^(o) is a metal ormetalloid selected from Groups 1-14 of the Periodic Table of theElements, R^(c) independently each occurrence is hydrogen or a grouphaving from 1 to 80 nonhydrogen atoms which is hydrocarbyl,hydrocarbylsilyl, trihydrocarbylsilyl, trihydrocarbylgermyl orhydrocarbylsilylhydrocarbyl; X^(a) is a noninterfering group having from1 to 100 nonhydrogen atoms which is halo-substituted hydrocarbyl,hydrocarbylamino-substituted hydrocarbyl, hydrocarbyloxy-substitutedhydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy orhalide; x is a nonzero integer which may range from 1 to an integerequal to the valence of M^(o); y is zero or a nonzero integer which mayrange from 1 to an integer equal to 1 less than the valence of M^(o);and x+y equals the valence of M^(o).
 44. The method of claim 43, whereinthe organometal or metalloid compound is an alumoxane or a mixture of analumoxane with M^(o)R^(c) _(x)X_(a) _(y).
 45. An addition polymerizationprocess wherein one or more addition polymerizable monomers arecontacted with a catalyst of claim 10 under addition polymerizationconditions.
 46. The addition polymerization process of claim 45 which isa solution, slurry phase or gas phase polymerization process.
 47. Theaddition polymerization process of claim 45, wherein the additionpolymerization reactor is operated under slurry phase polymerizationconditions.
 48. The addition polymerization process of claim 45, whereinthe addition polymerization reactor is operated under gas phasepolymerization conditions.